Catalyst for production of acetic acid or acetic acid and ethyl acetate, process for its production and process for production of acetic acid or acetic acid and ethyl acetate using it

ABSTRACT

An acetic acid production catalyst that contains (b) at least one element selected from the group consisting of Group 14 elements, Group 15 elements and Group 16 elements of the Periodic Table and/or (c) at least one element selected from the group consisting of Group 6 elements, Group 7 elements, Group 8 elements, Group 9 elements, Group 10 elements, Group 11 elements and Group 12 elements of the Periodic Table, added to a palladium-loaded catalyst, as well as an acetic acid and ethyl acetate production catalyst that contains (b) at least one compound selected from the group consisting of inorganic acids and salts thereof and/or (c) at least one element selected from the group consisting of Group 14 elements, Group 15 elements and Group 16 elements of the Periodic Table and/or (d) at least one element selected from the group consisting of Group 6 elements, Group 7 elements, Group 8 elements, Group 9 elements, Group 10 elements, Group 11 elements and Group 12 elements of the Periodic Table, added to palladium.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a divisional of Application Ser. No. 09/554,752, filed May 19,2000 now U.S. Pat. No. 6,552,220, the Disclosure of which isincorporated herein by reference, which was the National Stage ofInternational Application No. PCT/JP00/02203, filed Apr. 5, 2000, whichclaims benefit of Provisional Application No. 60/134,847, filed May 19,1999 and Provisional Application No. 60/160,004, filed Oct. 18, 1999.

TECHNICAL FIELD

The present invention relates to a catalyst for production of aceticacid or acetic acid and ethyl acetate from ethanol and oxygen, to aprocess for its production and to a process for production of aceticacid or acetic acid and ethyl acetate using the catalyst.

BACKGROUND ART

Processes for industrial production of acetic acid that have beenrealized include a process using oxidation of acetaldehyde, a processusing a reaction of methanol and carbon monoxide and a process usingoxidation of lower paraffins. Processes for industrial production ofethyl acetate that have been realized include an esterification reactionof ethanol and acetic acid, and a dimerization reaction of acetaldehyde.

In recent years, various production processes for acetic acid usingethanol as the starting material have been studied as an alternative.

An example of a process for obtaining acetic acid from ethanol in asingle stage which employs copper oxide as the main catalyst incombination with zinc oxide, chromium oxide and (chromiumoxide-manganese oxide) (Japanese Unexamined Patent Publication No.57-102835) has been disclosed. However, this process has been difficultto apply on an industrially practical scale because the reactiontemperature is high at 260-360° C., and the acetic acid selectivity isnot sufficient.

Oxidation processes with catalysts of platinum group metals,particularly palladium, have also been disclosed. For example, aceticacid can be obtained by reacting a catalyst of metallic palladium orpalladium loaded on a carrier such as silica or alumina (JapaneseExamined Patent Publication No. 48-19292, Brazil Patent BR-9104562) withethanol and oxygen. Palladium catalysts offer the advantage of arelatively low reaction temperature of 100-200° C. However, theseprocesses have all had the drawback of abundant by-products such asacetaldehyde and carbon dioxide, which have lowered the yield of thetarget acetic acid.

Processes using metallic palladium-loaded catalysts have been disclosedas processes for obtaining ethyl acetate from ethanol by a single stage.For example, according to Kunugi and Matsuura et al. (Kogyo KagakuZasshi, Vol. 71, No. 9, p. 1517 (1968)), ethyl acetate is obtained fromethanol and oxygen in the vapor phase using a catalyst of metallicpalladium loaded on a carrier of active carbon, γ-alumina or the like.Ethyl acetate is also obtained from ethanol and oxygen using a metallicpalladium/γ-alumina catalyst (Brazil Patent BR-8901776). However, theseprocesses have had the disadvantage of a low conversion rate of ethanoland abundant by-products such as acetaldehyde, methane and carbondioxide, which have lowered yields of the target ethyl acetate.

There has also been disclosed a catalyst including a palladium componentand crystalline titanium pyrophosphate represented by (TiP₂O₇) (JapaneseUnexamined Patent Publication No. 4-300851). Here, improvement in ethylacetate production activity has been reported by use of this binarycatalyst having palladium and titanium pyrophosphate as essentialcomponents, but even this process has low ethyl acetate productionactivity and selectivity, and is inadequate in practical terms on anindustrial scale.

On the other hand, processes employing palladium as the catalyst allowacetic acid and/or ethyl acetate to be obtained from ethanol and oxygenunder relatively mild reaction conditions. Notwithstanding, forindustrial scale production, a catalyst that is capable of catalyzingthe reaction with even higher activity and higher selectivity isstrongly desired.

DISCLOSURE OF INVENTION

It is an object of the present invention to provide a catalyst to beused for production of acetic acid or acetic acid and ethyl acetate fromethanol and oxygen, a process for its production, and a process forproduction of acetic acid or acetic acid and ethyl acetate using thecatalyst.

In order to achieve this object, the present inventors have conducteddiligent research aimed at further increasing catalyst performance in aprocess for producing acetic acid or acetic acid and ethyl acetate fromethanol and oxygen using a palladium catalyst, and as a result we havecompleted the present invention upon finding a catalyst with very lowcarbon dioxide selectivity, high activity and a long service life.

Specifically, the invention (I) is a catalyst for production of aceticacid, which is a catalyst used in a process for production of aceticacid by reaction of ethanol and oxygen that comprises (a) metallicpalladium and (b) at least one element selected from the groupconsisting of Group 14 elements, Group 15 elements and Group 16 elementsof the Periodic Table, held on a carrier.

The invention (II) is a catalyst for production of acetic acid, which isa catalyst used in a process for production of acetic acid by reactionof ethanol and oxygen that comprises (a) metallic palladium and (c) atleast one element selected from the group consisting of Group 6elements, Group 7 elements, Group 8 elements, Group 9 elements, Group 10elements, Group 11 elements and Group 12 elements of the Periodic Table,held on a carrier.

The invention (III) is a catalyst for production of acetic acid, whichis a catalyst used in a process for production of acetic acid byreaction of ethanol and oxygen that comprises (a) metallic palladium,(b) at least one element selected from the group consisting of Group 14elements, Group 15 elements and Group 16 elements of the Periodic Tableand (c) at least one element selected from the group consisting of Group6 elements, Group 7 elements, Group 8 elements, Group 9 elements, Group10 elements, Group 11 elements and Group 12 elements of the PeriodicTable, held on a carrier.

The invention (IV) is a process for production of a catalyst accordingto any one of the inventions (I) to (III).

The invention (V) is a process for production of acetic acid fromethanol and oxygen using a catalyst according to any one of theinventions (I) to (III).

The invention (VI) is a catalyst for production of acetic acid and ethylacetate, which is a catalyst used in a process for production of aceticacid and ethyl acetate by reaction of ethanol and oxygen that comprises(a) metallic palladium and (b) at least one compound selected-from thegroup consisting of inorganic acids and salts thereof.

The invention (VII) is a catalyst for production of acetic acid andethyl acetate, which is a catalyst used in a process for production ofacetic acid and ethyl acetate by reaction of ethanol and oxygen thatcomprises (a) metallic palladium, (b) at least one compound selectedfrom the group consisting of inorganic acids and salts thereof, and (c)at least one element selected from the group consisting of Group 14elements, Group 15 elements and Group 16 elements of the Periodic Table.

The invention (VIII) is a catalyst for production of acetic acid andethyl acetate, which is a catalyst used in a process for production ofacetic acid and ethyl acetate by reaction of ethanol and oxygen thatcomprises (a) metallic palladium, (b) at least one compound selectedfrom the group consisting of inorganic acids and salts thereof, and (d)at least one element selected from the group consisting of Group 6elements, Group 7 elements, Group 8 elements, Group 9 elements, Group 10elements, Group 11 elements and Group 12 elements of the Periodic Table.

The invention (IX) is a catalyst for production of acetic acid and ethylacetate, which is a catalyst used in a process for production of aceticacid and ethyl acetate by reaction of ethanol and oxygen that comprises(a) metallic palladium, (b) at least one compound selected from thegroup consisting of inorganic acids and salts thereof, (c) at least oneelement selected from the group consisting of Group 14 elements, Group15 elements and Group 16 elements of the Periodic Table, and (d) atleast one element selected from the group consisting of Group 6elements, Group 7 elements, Group 8 elements, Group 9 elements, Group 10elements, Group 11 elements and Group 12 elements of the Periodic Table.

The invention (X) is a catalyst for production of acetic acid and ethylacetate according to any one of the inventions (VI) to (IX), wherein thecatalyst components are held on a carrier.

The invention (XI) is a process for production of a catalyst accordingto any one of the inventions (VI) to (IX) that is not held on a carrier.

The invention (XII) is a process for production of the carrier-heldcatalyst of the invention (X).

The invention (XIII) is a process for production of acetic acid andethyl acetate from ethanol and oxygen, using a catalyst according to anyone of the inventions (VI) to (X).

BEST MODE FOR CARRYING OUT THE INVENTION

A catalyst for production of acetic acid according to the invention (I)will be explained first. The catalyst of the invention (I) is a catalystfor production of acetic acid which is a catalyst used in a process forproduction of acetic acid by reaction of ethanol and oxygen thatcomprises (a) metallic palladium and (b) at least one element selectedfrom the group consisting of Group 14 elements, Group 15 elements andGroup 16 elements of the Periodic Table (hereinafter may be referred toas group (b) element), held on a carrier.

The palladium contained in the catalyst of the invention (I) is metallicpalladium, and it has a valency of 0. The metallic palladium can beobtained by using a reducing agent such as hydrazine, hydrogen or thelike to reduce a divalent and/or tetravalent palladium ion. All of thepalladium need not be in a metallic state.

As the (b) Group 14 elements, Group 15 elements and Group 16 elements ofthe Periodic Table used for the invention (I) there may be mentionedselenium, tellurium, antimony, tin, bismuth and lead, but there is norestriction to these. Tellurium, selenium, bismuth and antimony areparticularly preferred for the group (b) elements in terms of catalystperformance and practicality.

The carrier used for the catalyst of the invention (I) is notparticularly restricted, and it may be a common porous substancecommonly used for carriers. As preferred substances there may bementioned silica, alumina, silica-alumina, diatomaceous earth,montmorillonite and titania, or ion exchange resins, polymer-basedcarriers, etc. with silica being most preferred. The form of the carrieris not particularly restricted. Specifically there may be mentioned theforms of powder, spheres, pellets and the like, but there is nolimitation to these. The particle size of the carrier is not especiallyrestricted. The particle size of the carrier is preferably from about 1mm to about 10 mm, and more preferably 3 to 8 mm. When the reaction iscarried out by packing the catalyst into a cylindrical reactor, aparticle size that is under 1 mm will result in a large pressure losswhen the gas flows through, and this may result in problems such as aninability to achieve effective gas circulation. If the particle size isgreater than 10 mm, the reaction gas can no longer diffuse into thecatalyst interior, and this may impede effective catalytic reaction.

The pore volume of the carrier is not particularly restricted. It ispreferably a pore volume of from about 0.2 ml to about 2.0 ml, and morepreferably 0.3 to 1.5 ml, per gram of the carrier. There are noparticular restrictions on the specific surface area of the carrier. Itis preferably a specific surface area of 20 to 800 m², and morepreferably 50 to 500 m², per gram of the carrier. There are also noparticular restrictions on the pore diameter of the carrier. It ispreferably in the range of 1 to 2000 nm, and more preferably 3 to 800nm.

The catalyst for production of acetic acid according to the invention(I) is a binary catalyst containing (a) metallic palladium and a group(b) element. Although the structure of the catalyst has not been fullyelucidated, the palladium is metallic palladium and the group (b)element is in the form of a metal, a compound or an alloy with metallicpalladium, and when these are combined they are believed to exist veryclose together. The (a) metallic palladium and the group (b) elementtherefore interact expressing very high activity and selectivity.

The compositional ratio of the (a) metallic palladium and the one ormore group (b) elements is preferably (a) 1 gram:(b) 0.005 to 10 grams,and more preferably (a) 1 gram:(b) 0.01 to 5 grams.

The loading amount of the (a) metallic palladium with respect to thecarrier will differ depending on the particle size and pore structure ofthe carrier, but it is normally preferred to be in the range of 0.05-10wt % with respect to the carrier. Although the reaction will stillproceed adequately even if the palladium loading amount is under 0.1 wt%, this presents the risk of lower productivity. Also, although thereaction will still proceed adequately even if the amount is over 10 wt%, the high price of palladium renders this undesirable in economic andpractical terms. In practice, the range is more preferably 0.2-6 wt %.Here, “wt %” with respect to the carrier refers to the value of theweight of the metallic palladium divided by the weight of the carrier.

The loading amount of the group (b) element with respect to the carrierwill differ depending on the particle size and pore structure of thecarrier, but it is preferably in the range of 0.0001-3 wt %, and morepreferably in the range of 0.001-2.0 wt %, with respect to the carrier.Here, “wt %” with respect to the carrier refers to the value of theweight of the group (b) element divided by the weight of the carrier.

The amount of the components-in the catalyst according to the invention(I) can be measured in the following manner. After pulverizing aprescribed amount of the catalyst with a mortar or the like into auniform powder, it is added to an acid such as hydrofluoric acid or aquaregia and dissolved by heating and stirring to prepare a homogeneoussolution. The solution is then quantitatively analyzed with a plasmaemission analyzer apparatus (for example, an SPS-1700 manufactured bySeiko Electronic Industries, KK.). The precision of the apparatus can beeasily adjusted with commercially available standard reagents ofdifferent elements, and repeatable quantitation is possible.

A catalyst for production of acetic acid according to the invention (II)will now be explained. The catalyst of the invention (II) is a catalystfor production of acetic acid which is a catalyst used in a process forproduction of acetic acid by reaction of ethanol and oxygen thatcomprises (a) metallic palladium and (c) at least one element selectedfrom the group consisting of Group 6 elements, Group 7 elements, Group 8elements, Group 9 elements, Group 10 elements, Group 11 elements andGroup 12 elements of the Periodic Table (hereinafter may be referred toas group (c) element), held on a carrier.

The (a) metallic palladium in the catalyst of the invention (II) is thesame as for the catalyst of the invention (I). The carrier is also thesame as for the catalyst of the invention (I).

The (c) Group 6 elements, Group 7 elements, Group 8 elements, Group 9elements, Group 10 elements, Group 11 elements and Group 12 elements ofthe Periodic Table used in the catalyst of the invention (II) include,specifically, chromium, zinc, gold, nickel, ruthenium and the like, butthere is no restriction to these. As preferred group (c) elements fromthe standpoint of catalyst performance and practicality there may bementioned zinc, gold and chromium.

The catalyst for production of acetic acid according to the invention(II) is a binary catalyst containing (a) metallic palladium and a group(c) element. Although the structure of the catalyst has not been fullyelucidated, the palladium is metallic palladium and the group (c)element is in the form of a metal, a compound or an alloy with metallicpalladium, and when these are combined they are believed to exist veryclose together. The (a) metallic palladium and the group (c) elementtherefore interact expressing very high activity and selectivity, andexhibiting very low carbon dioxide selectivity with excellent aceticacid production activity and selectivity, compared to prior artcatalysts.

The compositional ratio of the (a) metallic palladium and the one ormore group (c) elements in the catalyst of the invention (II) ispreferably (a) 1 gram:(c) 0.005 to 10 grams, and more preferably (a) 1gram:(c) 0.01 to 5 grams.

The loading amount of the (a) metallic palladium with respect to thecarrier is the same as for the catalyst of the invention (I).

The loading amount of the group (c) element with respect to the carrierwill differ depending on the particle size and pore structure of thecarrier, but it is preferably in the range of 0.0001-3 wt %, and morepreferably in the range of 0.001-2 wt %, with respect to the carrier.Here, “wt %” with respect to the carrier refers to the value of theweight of the group (c) element divided by the weight of the carrier.

The amount of the components in the catalyst according to the invention(II) can be measured by the same method as for the catalyst of theinvention (I).

A catalyst for production of acetic acid according to the invention(III) will now be explained. The catalyst of the invention (III) is acatalyst for production of acetic acid which is a catalyst used in aprocess for production of acetic acid by reaction of ethanol and oxygenthat comprises (a) metallic palladium, (b) at least one element selectedfrom the group consisting of Group 14 elements, Group 15 elements andGroup 16 elements of the Periodic Table and (c) at least one elementselected from the group consisting of Group 6 elements, Group 7elements, Group 8 elements, Group 9 elements, Group 10 elements, Group11 elements and Group 12 elements of the Periodic Table, held on acarrier.

The (a) metallic palladium in the catalyst of the invention (III) is thesame as for the catalyst of the invention (I).

Also, in the catalyst of the invention (III), the (b) Group 14 elements,Group 15 elements and Group 16 elements of the Periodic Table are thesame as for the catalyst of the invention (I), and the (c) Group 6elements, Group 7 elements, Group 8 elements, Group 9 elements, Group 10elements, Group 11 elements and Group 12 elements of the Periodic Tableare the same as for the catalyst of the invention (II). The carrier isalso the same as for the catalyst of the invention (II).

The catalyst for production of acetic acid according to the invention(III) is a ternary catalyst containing (a) metallic palladium, a group(b) element and a group (c) element. Although the structure of thecatalyst has not been fully elucidated, the palladium is metallicpalladium, and the group (b) element and the group (c) element are eachin the form of a metal, a compound or an alloy with metallic palladium,and when these are combined they are believed to exist very closetogether. The (a) metallic palladium, the group (b) element and thegroup (c) element therefore interact expressing very high activity andselectivity, and exhibiting very low carbon dioxide selectivity withexcellent acetic acid production activity and selectivity, compared toprior art catalysts.

The compositional ratio of the (a) metallic palladium, the one or moregroup (b) elements and the one or more group (c) elements in thecatalyst of the invention (III) is preferably (a) 1 gram:(b) 0.005-10grams:(c) 0.005 to 10 grams, and more preferably (a) 1 gram:(b) 0.01-5.0grams:(c) 0.01 to 5 grams.

The loading amount of the (a) metallic palladium and the loading amountof the group (b) element with respect to the carrier are the same as forthe catalyst of the invention (I), and the loading amount of the group(c) element is the same as for the catalyst of the invention (II).

The amount of the components in the catalyst according to the invention(III) can be measured by the same method as for the catalyst of theinvention (I).

The process of the invention (IV) will now be explained. The process ofthe invention (IV) is a process for production of a catalyst forproduction of acetic acid according to the invention (I), (II) or (III).

The catalyst for production of acetic acid according to the invention(I) can be produced by the following production process (1) or (2).

Production process (1) for a catalyst for production of acetic acidaccording to the invention (I) comprises the following steps 1 and 2.

Step 1

A step wherein the (a) metallic palladium is loaded on a carrier toobtain a metallic palladium-loaded catalyst.

Step 2

A step wherein (b) at least one element selected from the groupconsisting of Group 14 elements, Group 15 elements and Group 16 elementsof the Periodic Table is loaded on the metallic palladium-loadedcatalyst obtained in step 1 to obtain a catalyst for production ofacetic acid.

Production process (2) for a catalyst for production of acetic acidaccording to the invention (I) comprises the following steps 1 and 2.

Step 1

A step wherein a palladium compound and (b) at least one elementselected from the group consisting of Group 14 elements, Group 15elements and Group 16 elements of the Periodic Table are loaded on acarrier to obtain a palladium compound-loaded catalyst.

Step 2

A step wherein the palladium compound-loaded catalyst obtained in step 1is reduced to obtain a catalyst for production of acetic acid.

In step 1 of production process (1) for a catalyst for production ofacetic acid according to the invention (I), the palladium compoundserving as the starting material for the metallic palladium is notparticularly restricted. In most cases it is possible to use compoundsthat can be converted to palladium metal, for example, halides such aspalladium chloride, organic acid salts such as palladium acetate, andalso palladium nitrate, palladium oxide, palladium sulfate and sodiumtetrachloropalladate, as well as palladium metal itself.

There are no particular restrictions on the method of loading themetallic palladium or the palladium compound that can be converted tometallic palladium on the carrier, and it may be loaded by any method.For example, when loading a palladium compound that can be converted tometallic palladium, the palladium compound may be dissolved or suspendedin an appropriate solvent such as water or acetone, in an inorganic acidor organic acid such as hydrochloric acid, nitric acid, acetic acid, orthe like, or a solution thereof, and then loaded onto the carrier anddried, as the method of loading onto the carrier.

As loading means there may be mentioned the impregnation method,evaporation to dry hardness method, kneading method and spray method,but there is no limitation to these.

When loading a palladium compound that can be converted to metallicpalladium, there are no particular restrictions on the method ofsubsequently converting the palladium compound to metallic palladium,i.e. the method of reduction treatment. The reduction treatment may becarried out in either a liquid phase or vapor phase state, with noparticular restrictions so long as the conditions are common reducingconditions.

Liquid phase reduction treatment is usually carried out at roomtemperature, but it may also be conducted with heating to a highertemperature of, specifically, about 30-50° C. Vapor phase reductiontreatment is preferably carried out with heating of the palladiumcompound-loaded carrier to about 100-600° C. in order to achieve totalconversion to palladium metal.

Specifically there may be mentioned a method whereby the palladiumcompound is reduced to metallic palladium by hydrazine, formalin,hydrogen, methanol, ethylene or the like, either directly or aftertreatment with an aqueous solution of sodium hydroxide, potassiumhydroxide, barium hydroxide, sodium metasilicate, etc. to convert thepalladium compound to an oxide, hydroxide, or the like.

The procedure for conversion of the palladium compound that can beconverted to metallic palladium into metallic palladium may be carriedout after separating the catalyst carrying the palladium compound, or itmay be carried out immediately following the loading procedure. Ifconditions permit, it is preferably carried out immediately followingthe loading procedure, without separation. If necessary, the metallicpalladium-loaded catalyst may be filtered by a common method and thenwashed and dried to remove any reaction-inhibiting substances for thecatalytic reaction, such as halides or alkali salts of sodium, etc.

The metallic palladium-loaded catalyst can be obtained in the mannerdescribed above.

Step 2 of production process (1) for a catalyst for production of aceticacid according to the invention (I) is a step wherein (b) at least oneelement selected from the group consisting of Group 14 elements, Group15 elements and Group 16 elements of the Periodic Table is loaded on themetallic palladium-loaded catalyst obtained in step 1 to obtain acatalyst for production of acetic acid.

The starting material of the (b) at least one element selected from thegroup consisting of Group 14 elements, Group 15 elements and Group 16elements of the Periodic Table is not particularly restricted, and itmay be the element itself or a halide, nitrate, acetate, phosphate,sulfate or oxide containing the element, or even a complex with anorganic molecule such as acetylacetonato or nitrile as the ligand.

Specifically there may be mentioned chlorides such as selenium chloride,tellurium chloride, antimony chloride, tin chloride, bismuth chloride,lead chloride, etc.; nitrates such as antimony nitrate, tin nitrate,bismuth nitrate, lead nitrate, etc.; acetates such as tin acetate,bismuth acetate, lead acetate, etc.; and selenium oxide, selenic acid(H₂SeO₄) and its salts, selenious acid (H₂SeO₃) and its salts, metallicselenium, tellurium oxide, telluric acid (H₆TeO₆) and its salts,tellurous acid (H₂TeO₃) and its salts, metallic tellurium and the like,but there is no limitation to these.

There are no particular restrictions on the method of loading thestarting material for the group (b) element on the carrier, and it maybe loaded by any method. For example, the starting material for thegroup (b) element may be dissolved or suspended in an appropriatesolvent such as water or acetone, or in an inorganic acid or organicacid such as hydrochloric acid, nitric acid, acetic acid, or the likeand then impregnated into the carrier and dried, as the method ofloading onto the carrier.

As loading means there may be mentioned the impregnation method,evaporation to dry hardness method, kneading method and spray method,but there is no limitation to these.

A catalyst for production of acetic acid according to the invention (I)can be obtained in the manner described above.

Step 1 of production process (2) for a catalyst for production of aceticacid according to the invention (I) is a step wherein a palladiumcompound and (b) at least one element selected from the group consistingof Group 14 elements, Group 15 elements and Group 16 elements of thePeriodic Table are loaded on a carrier to obtain a palladiumcompound-loaded catalyst.

In step 1 of production process (2) for a catalyst for production ofacetic acid according to the invention (I), the palladium compoundserving as the starting material for the metallic palladium and itsloading method are the same as in step 1 of production process (1) for acatalyst for production of acetic acid according to the invention (I).

The starting material for the group (b) element and its loading methodare also the same as in step 2 of production process (1) for a catalystfor production of acetic acid according to the invention (I).

The loading of the palladium compound that can be converted to metallicpalladium on the carrier and the loading of the starting material forthe group (b) element on the carrier may be carried out in any order.That is, both loadings may be carried out simultaneously, or one beforethe other. However, it is preferred for loading of the group (b) elementon the carrier to be carried out simultaneously with loading of thepalladium compound.

The palladium compound-loaded catalyst can be obtained in the mannerdescribed above.

Step 2 of production process (2) for a catalyst for production of aceticacid according to the invention (I) is a step wherein the palladiumcompound-loaded catalyst obtained in step 1 is reduced to obtain acatalyst for production of acetic acid.

For a catalyst having a palladium compound that can be converted tometallic palladium and/or a starting compound for a group (b) elementheld on a carrier, the method for conversion of these compounds to theirrespective metal elements, i.e. the method of reduction treatment, isnot particularly restricted. The reduction treatment is the same as instep 1 of production process (1) for a catalyst for production of aceticacid according to the invention (I).

A catalyst for production of acetic acid according to the invention (I)can be obtained in the manner described above.

A catalyst for production of acetic acid according to the invention (II)can be produced by the following production process (3) or (4).

Production process (3) for a catalyst for production of acetic acidaccording to the invention (II) comprises the following steps 1 and 2.

Step 1

A step wherein the (a) metallic palladium is loaded on a carrier toobtain a metallic palladium-loaded catalyst.

Step 2

A step wherein (c) at least one element selected from the groupconsisting of Group 6 elements, Group 7 elements, Group 8 elements,Group 9 elements, Group 10 elements, Group 11 elements and Group 12elements of the Periodic Table is loaded on the metallicpalladium-loaded catalyst obtained in step 1 to obtain a catalyst forproduction of acetic acid.

Production process (4) for a catalyst for production of acetic acidaccording to the invention (II) comprises the following steps 1 and 2.

Step 1

A step wherein a palladium compound and (c) at least one elementselected from the group consisting of Group 6 elements, Group 7elements, Group 8 elements, Group 9 elements, Group 10 elements, Group11 elements and Group 12 elements of the Periodic Table are loaded on acarrier to obtain a palladium compound-loaded catalyst.

Step 2

A step wherein the palladium compound-loaded catalyst obtained in step 1is reduced to obtain a catalyst for production of acetic acid.

In step 1 of production process (3) for a catalyst for production ofacetic acid according to the invention (II), the palladium compoundserving as the starting material for the metallic palladium, its loadingmethod and the method for its conversion to metallic palladium are thesame as in step 1 of production process (1) for a catalyst forproduction of acetic acid according to the invention (I).

Step 2 in production process (3) for a catalyst for production of aceticacid according to the invention (II) is step wherein (c) at least oneelement selected from the group consisting of Group 6 elements, Group 7elements, Group 8 elements, Group 9 elements, Group 10 elements, Group11 elements and Group 12 elements of the Periodic Table is loaded on themetallic palladium-loaded catalyst obtained in step 1 to obtain acatalyst for production of acetic acid.

The (c) at least one element selected from the group consisting of Group6 elements, Group 7 elements, Group 8 elements, Group 9 elements, Group10 elements, Group 11 elements and Group 12 elements of the PeriodicTable is not particularly restricted, and it may be the element itselfor a halide, nitrate, acetate, phosphate, sulfate or oxide containingthe element, or even a complex with an organic molecule such asacetylacetonato or nitrile as the ligand.

Specifically there may be mentioned chlorides such as chromium chloride,manganese chloride, rhenium chloride, ruthenium chloride, rhodiumchloride, iridium chloride, nickel chloride, tetrachloro aurate and itssalts, chlorides such as zinc chloride, etc.; nitrates such as chromiumnitrate, manganese nitrate, nickel nitrate, iridium nitrate, zincnitrate, etc.; acetates such as chromium acetate, manganese acetate,rhenium acetate, ruthenium acetate, iridium acetate, nickel acetate,zinc acetate, and the like, but there is no limitation to these.

There are no particular restrictions on the method of loading thestarting material for the group (c) element on the carrier, and it maybe loaded by any method. For example, the starting material for thegroup (c) element may be dissolved or suspended in an appropriatesolvent such as water or acetone, or in an inorganic acid or organicacid such as hydrochloric acid, nitric acid, acetic acid or the like andthen impregnated into the carrier and dried, as the method of loadingonto the carrier. As loading means there may be mentioned theimpregnation method, evaporation to dry hardness method, kneading methodand spray method, but there is no limitation to these.

A catalyst for production of acetic acid according to the invention (II)can be obtained in the manner described above.

Step 1 in production process (4) for a catalyst for production of aceticacid according to the invention (II) is a step wherein a palladiumcompound and (c) at least one element selected from the group consistingof Group 6 elements, Group 7 elements, Group 8 elements, Group 9elements, Group 10 elements, Group 11 elements and Group 12 elements ofthe Periodic Table are loaded on a carrier to obtain a palladiumcompound-loaded catalyst.

In production process (4) for a catalyst for production of acetic acidaccording to the invention (II), the palladium compound serving as thestarting material for the metallic palladium and its loading method arethe same as in step 1 of production process (1) for a catalyst forproduction of acetic acid according to the invention (I).

The starting material for the group (c) element and its loading methodare the same as in step 2 of production process (i) for a catalyst forproduction of acetic acid according to the invention (II).

The loading of the palladium compound that can be converted to metallicpalladium on the carrier and the loading of the starting material forthe group (c) element on the carrier may be carried out in any order.That is, both loadings may be carried out simultaneously, or one beforethe other. However, it is preferred for loading of the group (c) elementon the carrier to be carried out simultaneously with loading of thepalladium compound.

Step 2 in production process (4) for a catalyst for production of aceticacid according to the invention (II) is step wherein the palladiumcompound-loaded catalyst obtained in step 1 is reduced to obtain acatalyst for production of acetic acid.

For a catalyst having a palladium compound that can be converted tometallic palladium and/or a starting compound for a group (c) elementheld on a carrier, the method for conversion of these compounds to theirrespective metal elements, i.e. the method of reduction treatment, isnot particularly restricted. The reduction treatment is the same as instep 1 of production process (1) for a catalyst for production of aceticacid according to the invention (I).

A catalyst for production of acetic acid according to the invention (II)can be obtained in the manner described above.

A catalyst for production of acetic acid according to the invention(III) can be produced by the following production process (5) to (8).

Production process (5) for a catalyst for production of acetic acidaccording to the invention (III) comprises the following steps 1 and 2.

Step 1

A step wherein metallic palladium is loaded on a carrier to obtain ametallic palladium-loaded catalyst.

Step 2

A step wherein (b) at least one element selected from the groupconsisting of Group 14 elements, Group 15 elements and Group 16 elementsof the Periodic Table and (c) at least one element selected from thegroup consisting of Group 6 elements, Group 7 elements, Group 8elements, Group 9 elements, Group 10 elements, Group 11 elements andGroup 12 elements of the Periodic Table are loaded on the metallicpalladium-loaded catalyst obtained in step 1 to obtain a catalyst forproduction of acetic acid.

Production process (6) for a catalyst for production of acetic acidaccording to the invention (III) comprises the following steps 1 and 2.

Step 1

A step wherein a palladium compound, (b) at least one element selectedfrom the group consisting of Group 14 elements, Group 15 elements andGroup 16 elements of the Periodic Table and (c) at least one elementselected from the group consisting of Group 6 elements, Group 7elements, Group 8 elements, Group 9 elements, Group 10 elements, Group11 elements and Group 12 elements of the Periodic Table are loaded on acarrier to obtain a palladium compound-loaded catalyst.

Step 2

A step wherein the palladium compound-loaded catalyst obtained in step 1is reduced to obtain a catalyst for production of acetic acid.

Production process (7) for a catalyst for production of acetic acidaccording to the invention (III) comprises the following steps 1 to 3.

Step 1

A step wherein a palladium compound and (b) at least one elementselected from the group consisting of Group 14 elements, Group 15elements and Group 16 elements of the Periodic Table are loaded on acarrier to obtain a palladium compound-loaded catalyst.

Step 2

A step wherein the palladium compound-loaded catalyst obtained in step 1is reduced to obtain a metallic palladium-loaded catalyst.

Step 3

A step wherein (c) at least one element selected from the groupconsisting of Group 6 elements, Group 7 elements, Group 8 elements,Group 9 elements, Group 10 elements, Group 11 elements and Group 12elements of the Periodic Table is loaded on the metallicpalladium-loaded catalyst obtained in step 2 to obtain a catalyst forproduction of acetic acid.

Production process (8) for a catalyst for production of acetic acidaccording to the invention (III) comprises the following steps 1 to 3.

Step 1

A step wherein a palladium compound and (c) at least one elementselected from the group consisting of Group 6 elements, Group 7elements, Group 8 elements, Group 9 elements, Group 10 elements, Group11 elements and Group 12 elements of the Periodic Table are loaded on acarrier to obtain a palladium compound-loaded catalyst.

Step 2

A step wherein the palladium compound-loaded catalyst obtained in step 1is reduced to obtain a metallic palladium-loaded catalyst.

Step 3

A step wherein (b) at least one element selected from the groupconsisting of Group 14 elements, Group 15 elements and Group 16 elementsof the Periodic Table is loaded on the metallic palladium-loadedcatalyst obtained in step 2 to obtain a catalyst for production ofacetic acid.

In step 1 of production process (5) for a catalyst for production ofacetic acid according to the invention (III), the palladium compoundserving as the starting material for the metallic palladium, its loadingmethod and the method for its conversion to metallic palladium are thesame as in step 1 of production process (1) for a catalyst forproduction of acetic acid according to the invention (I).

In step 2 of production process (5) for a catalyst for production ofacetic acid according to the invention (III), the starting material forthe (b) at least one element selected from the group consisting of Group14 elements, Group 15 elements and Group 16 elements of the PeriodicTable and its loading method are the same as in step 2 of productionprocess (1) for a catalyst for production of acetic acid according tothe invention (I).

The starting material for the group (c) element and its loading methodare the same as in step 2 of production process (3) for a catalyst forproduction of acetic acid according to the invention (II).

A catalyst for production of acetic acid according to the invention(III) can be obtained in the manner described above.

In step 1 of production process (6) for a catalyst for production ofacetic acid according to the invention (III), the palladium compoundserving as the starting material for the metallic palladium and itsloading method are the same as in step 1 of production process (1) for acatalyst for production of acetic acid according to the invention (I).

The starting material for the group (b) element and its loading methodare the same as in step 2 of production process (1) for a catalyst forproduction of acetic acid according to the invention (I).

The starting material for the group (c) element and its loading methodare the same as in step 2 of production process (3) for a catalyst forproduction of acetic acid according to the invention (II).

The loading of the palladium compound that can be converted to metallicpalladium on the carrier, the loading of the starting material for thegroup (b) element on the carrier and the loading of the startingmaterial for the group (c) element on the carrier may be carried out inany order. That is, all of the loadings may be carried outsimultaneously, or one before the others. However, it is preferred forloading of the group (c) element on the carrier to be carried outsimultaneously with loading of the palladium compound.

The palladium compound-loaded catalyst can be obtained in the mannerdescribed above.

Step 2 of production process (6) for a catalyst for production of aceticacid according to the invention (III) is a step wherein the palladiumcompound-loaded catalyst obtained in step 1 is reduced to obtain acatalyst for production of acetic acid.

For a catalyst having a palladium compound that can be converted tometallic palladium, a starting compound for a group (b) element and astarting compound for a group (c) element held on a carrier, the methodfor conversion of these compounds to their respective metal elements,i.e. the method of reduction treatment, is not particularly restricted.The reduction treatment is the same as in step 1 of production process(1) for a catalyst for production of acetic acid according to theinvention (I).

In step 1 of production process (7) for a catalyst for production ofacetic acid according to the invention (III), the palladium compoundserving as the starting material for the metallic palladium and itsloading method are the same as in step 1 of production process (1) for acatalyst for production of acetic acid according to the invention (I).

The starting material for the group (b) element and its loading methodare the same as in step 2 of production process (1) for a catalyst forproduction of acetic acid according to the invention (I).

The loading of the palladium compound that can be converted to metallicpalladium on the carrier and the loading of the starting material forthe group (b) element on the carrier may be carried out in any order.That is, both loadings may be carried out simultaneously, or one beforethe other. However, it is preferred for loading of the group (b) elementon the carrier to be carried out simultaneously with loading of thepalladium compound.

The palladium compound-loaded catalyst can be obtained in the mannerdescribed above.

Step 2 of production process (7) for a catalyst for production of aceticacid according to the invention (III) is a step wherein the palladiumcompound-loaded catalyst obtained in step 1 is reduced to obtain ametallic palladium-loaded catalyst.

For a catalyst having a palladium compound that can be converted tometallic palladium and a starting compound for a group (b) element heldon a carrier, the method for conversion of these compounds to theirrespective metal elements, i.e. the method of reduction treatment, isnot particularly restricted. The reduction treatment is the same as instep 1 of production process (1) for a catalyst for production of aceticacid according to the invention (I).

The metallic palladium-loaded catalyst can be obtained in the mannerdescribed above.

Step 3 of production process (7) for a catalyst for production of aceticacid according to the invention (III) is a step wherein a group (c)element is loaded on the metallic palladium-loaded catalyst obtained instep 2 to obtain a catalyst for production of acetic acid.

The starting material for the group (c) element and its loading methodare the same as in step 2 of production process (3) for a catalyst forproduction of acetic acid according to the invention (II).

A catalyst for production of acetic acid according to the invention(III) can be obtained in the manner described above.

In step 1 of production process (8) for a catalyst for production ofacetic acid according to the invention (III), the palladium compoundserving as the starting material for the metallic palladium and itsloading method are the same as in step 1 of production process (3) for acatalyst for production of acetic acid according to the invention (II).

The starting material for the group (c) element and its loading methodare the same as in step 2 of production process (3) for a catalyst forproduction of acetic acid according to the invention (II).

The loading of the palladium compound that can be converted to metallicpalladium on the carrier and the loading of the starting material forthe group (c) element on the carrier may be carried out in any order.That is, both loadings may be carried out simultaneously, or one beforethe other. However, it is preferred for loading of the group (c) elementon the carrier to be carried out simultaneously with loading of thepalladium compound.

The palladium compound-loaded catalyst can be obtained in the mannerdescribed above.

Step 2 of production process (8) for a catalyst for production of aceticacid according to the invention (III) is a step wherein the palladiumcompound-loaded catalyst obtained in step 1 is reduced to obtain ametallic palladium-loaded catalyst.

For a catalyst having a palladium compound that can be converted tometallic palladium and a starting compound for a group (c) element heldon a carrier, the method for conversion of these compounds to theirrespective metal elements, i.e. the method of reduction treatment, isnot particularly restricted. The reduction treatment is the same as instep 1 of production process (1) for a catalyst for production of aceticacid according to the invention (I).

The metallic palladium-loaded catalyst can be obtained in the mannerdescribed above.

Step 3 of production process (8) for a catalyst for production of aceticacid according to the invention (III) is a step wherein a group (b)element is loaded on the metallic palladium-loaded catalyst obtained instep 2 to obtain a catalyst for production of acetic acid.

The starting material for the group (b) element and its loading methodare the same as in step 2 of production process (1) for a catalyst forproduction of acetic acid according to the invention (I).

A catalyst for production of acetic acid according to the invention(III) can be obtained in the manner described above.

The invention (V) is a process for production of acetic acid fromethanol and oxygen using a catalyst for production-of acetic acidaccording to any one of the inventions (I), (II) or (III).

The reaction process is not particularly restricted so long as it allowsa catalyst of the invention to react ethanol with oxygen, and it may beany of a variety of processes including a batch process, semi-batchprocess, semi-continuous process, continuous flow process or acombination thereof, for a vapor phase reaction or liquid phasereaction.

The ethanol starting material may be supplied in liquid form, or it maybe supplied in vapor form. That is, the reaction process may be, forexample, a semi-continuous process whereby the catalyst of the inventionis suspended in liquid ethanol and/or an ethanol solution and oxygen ispassed through, or a continuous flow process whereby ethanol and oxygengas are passed through the catalyst. A vapor phase reaction process ispreferred from the standpoint of separation of the catalyst, startingmaterials and products, and from the standpoint of acetic acidproductivity. More preferred, and advantageous in practical terms, is toemploy a fixed bed having corrosion-resistant reaction tubes packed withthe catalyst of the invention, for a vapor phase reaction process inwhich the ethanol and oxygen are passed through.

A vapor phase reaction and liquid phase reaction used in the process forproduction of acetic acid according to the invention (V) will now beexplained.

A vapor phase reaction will be explained first.

There are no particular restrictions on the reaction temperature forproduction of acetic acid by reaction of ethanol and oxygen in a vaporphase according to the acetic acid production method of the invention(V), but it is preferably 100-250° C. If the reaction temperature isbelow 100° C. the reaction rate may be insufficient, while if it isabove 250° C. a greater number of secondary reactions will tend tooccur. More preferred in practical terms is the range of 120-230° C.

The reaction pressure is not particularly restricted but in terms of theequipment it is advantageous in practice for it to be from 0.0 to 3.0MPa (gauge pressure). It is more preferably in the range of 0.1 to 1.5MPa (gauge pressure),

In the case of a flow-type reaction, the gas supplied to the reactionsystem comprises ethanol and oxygen, and if necessary nitrogen, carbondioxide, a rare gas or the like may also be used as a diluent. Theethanol is supplied to the reaction system in an amount corresponding toa proportion of 0.01-50% by volume, and especially 0.1-40% by volume,and the oxygen in an amount corresponding to a proportion of 1-15% byvolume, and especially 2-10% by volume, with respect to the total amountof supply gas. Here, an ethanol concentration exceeding 20% by volumewill tend to increase the degree of secondary reactions, while aconcentration of under 2% by volume will tend to lower the productivity.

The presence of water in the reaction system will provide a notableeffect of improved acetic acid production activity and selectivity, aswell as prolonged activity of the catalyst in the reaction system. It issuitable for water vapor to be included in the reaction gas at 0.1-50%by volume. If the water vapor in the reaction gas is present at lessthan 0.1% by volume the catalyst may tend to undergo deterioration morereadily, and if it is present at greater than 50% by volume, the steamunit requirement may be poorer. In practical terms, the range is mostpreferably 0.5-40% by volume.

When carrying out the production process for acetic acid of theinvention according to this gas phase reaction there are no particularrestrictions on the ethanol starting material. It is advantageous to usea high purity ethanol starting material, but there is no problem withmixing a small amount of a lower saturated hydrocarbon such as methane,ethane or propane or the like.

There are also no particular restrictions on the oxygen, and it may bein a form such as air, diluted with an inert gas such as nitrogen,carbon dioxide gas or the like. When the reaction gas is circulated itis generally more advantageous to use oxygen at a high concentration,preferably 99% or greater.

The reaction mixture gas consisting of ethanol and oxygen may be blendedwith acetaldehyde, diethyl ether or the like and supplied to thereaction system. Acetaldehyde and/or diethyl ether to be suppliedtogether with the reaction mixture gas may be in an amount of the rangeof preferably 0.001-5.0% by volume, more preferably 0.01-4.0% by volumein the total reaction mixture gas.

The reaction mixture gas is preferably passed through the catalyst at aspace velocity (SV) in the range of 500-15,000 hr⁻¹, and especially1000-10,000 hr⁻¹, in a standard state.

Next, a liquid phase reaction will be explained.

There are no particular restrictions on the reaction temperature forproduction of acetic acid by reaction of ethanol and oxygen in a liquidphase according to the acetic acid production method of the invention(V), but it is preferably 0-200° C. If the reaction temperature is below0° C. the reaction rate may be insufficient, while if it is above 200°C. a greater number of secondary reactions may occur. More preferred inpractical terms is the range of 20-100° C.

The reaction pressure is not particularly restricted but in terms of theequipment it is advantageous in practice for it to be from 0.0 to 3.0MPa (gauge pressure). It is more preferably in the range of 0.1 to 1.5MPa (gauge pressure).

The ethanol and/or oxygen starting materials may be present in thecatalyst beforehand, or they may be added at an appropriate point duringthe reaction. When they are supplied to the reaction system, they may bein gaseous and/or liquid form.

The starting material supplied to the reaction system comprises ethanoland oxygen, and if necessary nitrogen, carbon dioxide or a diluting gasmay also be used.

The presence of water in the reaction system will provide a notableeffect of improved acetic acid production activity and selectivity, aswell as prolonged activity of the catalyst in the reaction system. Theproportion of water and ethanol in the reaction system is notparticularly restricted. The proportion of water and ethanol may even bechanged during the reaction, or an appropriate amount of water may beadded to keep a constant proportion. If necessary, a basic componentsuch as sodium hydroxide may be added to increase the reaction rate.

When carrying out the production process for acetic acid of theinvention according to this liquid phase reaction there are noparticular restrictions on the ethanol starting material. It isadvantageous to use a high purity ethanol starting material, but thereis no problem with mixing a small amount of a lower saturatedhydrocarbon such as methane, ethane or propane or the like.

There are also no particular restrictions on the oxygen, and it may bein a form such as air, or diluted with an inert gas such as nitrogen,carbon dioxide gas or the like. When the reaction gas is circulated itis generally more advantageous to use oxygen at a high concentration,preferably 99% or greater.

The reaction mixture gas or liquid consisting of ethanol and oxygen maybe blended with acetaldehyde, diethyl ether or the like and supplied tothe reaction system.

The obtained acetic acid may be separated and purified by common methodsto the desired degree of purity, in the case of either a gas phasereaction or a liquid phase reaction. When unreacted starting materialsand by-products of acetaldehyde and/or diethyl ether remain, thoseunreacted starting materials and by-products of acetaldehyde and/ordiethyl ether can be recovered and recycled into the reaction system foruse.

When necessary, the catalyst used may be regenerated at an appropriatepoint or separated for repeated use.

A catalyst for production of acetic acid and ethyl acetate according tothe inventions (VI) and (X) will now be explained.

The invention (VI) is a non-carrier-held catalyst for production ofacetic acid and ethyl acetate, which is a catalyst used in a process forproduction of acetic acid and ethyl acetate by reaction of ethanol andoxygen that comprises (a) metallic palladium and (b) at least onecompound selected from the group consisting of inorganic acids and saltsthereof (hereinafter may be referred to as group (b) compound) or acarrier-held catalyst for production of acetic acid and ethyl acetatewherein these catalyst components are held on a carrier is one of thecatalysts according to the invention (X).

The palladium contained in the catalyst of the invention (VI) ismetallic palladium, and it has a valency of 0. The metallic palladiumcan be obtained by using a reducing agent such as hydrazine, hydrogen orthe like to reduce a divalent and/or tetravalent palladium ion. All ofthe palladium need not be in a metallic state.

As the inorganic acid of the group (b) compound there may be mentionedphosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, niobicacid, heteropoly acids and the like, but there is no limitation tothese. It is preferably phosphoric acid or a heteropoly acid.

A heteropoly acid is an acid formed by condensation of two or moreinorganic oxyacids comprising a coordinated element (poly atom) and acentral element (hetero atom). As the hetero atom in the heteropoly acidthere may be mentioned phosphorus, silicon, boron, aluminum, germanium,cerium, cobalt and chromium, and as the poly atom there may be mentionedmolybdenum, tungsten, vanadium, niobium and tantalum, but there are noparticular restrictions. As specific examples there may be mentionedtungstosilicic acid, tungstophosphoiic acid, molybdosilicic acid,molybdophosphoric acid, molybdotungstophosphoric acid,molybdotungatosilicic acid, vanadotungstophosphoric acid,vanadotungstosilicic acid, vanadomolybdosilicic acid,vanadomolybdophosphoric acid, tungstoboric acid, molybdoboric acid andmolybdotungstoboric acid.

Particularly preferred among these are heteropoly acids wherein thehetero atom is phosphorus or silicon and the polyatom is at least oneelement selected from the group consisting of tungsten, molybdenum andvanadium.

As the inorganic acid salt of the group (b) compound there may bementioned metal salts or onium salts wherein all or a portion of thehydrogen atoms of the inorganic acid are substituted.

The metal element substituting the hydrogen atoms of the inorganic acidis not particularly restricted. Specific examples are at least oneelement selected from the group consisting of Group 1, Group 2, Group 6,Group 7, Group 8, Group 9, Group 10, Group 11, Group 12 and Group 13elements of the Periodic Table, and examples of onium salts of theinorganic acid include ammonium salts with ammonium or amines.Particularly preferred among these inorganic acid salts are metal saltsof lithium, sodium, potassium, cesium, rubidium, chromium, barium,cobalt, nickel, manganese and copper.

While the structure of the catalyst has not been fully elucidated, thepalladium is (a) metallic palladium, and the group (b) compound is acompound with definite acidity. The elements and compounds of these twogroups (a) and (b) are believed to exist very close together, thecompounds and elements of each group interacting to express very highactivity and selectivity.

The compositional ratio of the (a) metallic palladium and the group (b)compound is preferably (a) 1 gram:(b) 0.025-500 grams and morepreferably (a) 1 gram:(b) 0.1-400 grams.

There are no particular restrictions on the content of the (a) metallicpalladium in the catalyst. However, it is preferably in the range of0.001-10 wt %. Although the reaction will still proceed adequately evenif the content of the (a) metallic palladium is under 0.001 wt %, thispresents the risk of lower practical productivity. Also, although thereaction will still proceed adequately even if the content of the (a)metallic palladium is over 10 wt %, the high price of palladium rendersthis undesirable in economic and practical terms. In practice, the rangeis more preferably 0.005-8.0 wt %. Here, “wt %” refers to the proportionof the weight of the (a) metallic palladium in the catalyst with respectto the weight of the total catalyst.

The catalyst may be effectively used with only the catalyst substancehaving the aforementioned composition, or it may be loaded on a carrierfor more advantageous use.

The carrier used is suitably porous silica, alumina, silica-alumina,diatomaceous earth, montmorillonite, titania, an ion exchange resin or apolymer-based carrier, with silica being most suitable. The carrier maybe in the form of a powder, spheres, pellets or any other desired form.

The particle size of the carrier is preferably 1-10 mm. When thereaction is carried out by packing the catalyst into a cylindricalreactor, a particle size that is under 1 mm will result in a largepressure loss when the gas flows through, and this may make itimpossible to achieve effective gas circulation. If the particle size isover 10 mm, the reaction gas can no longer diffuse into the catalystinterior, and this may impede effective catalytic reaction. The particlesize is more preferably 3-8 mm.

The pore volume of the carrier is preferably a pore volume of 0.2-2.0ml, and more preferably 0.3-1.5 ml, per gram of the carrier. Thespecific surface area of the carrier is preferably a specific surfacearea of 20-800 m², and more preferably 50-500 m², per gram of thecarrier. The pore diameter of the carrier is preferably 1-2000 nm, andmore preferably 3-800 nm.

The loading amount of the (a) metallic palladium with respect to thecarrier will differ depending on the particle size and pore structure ofthe carrier, but it is normally preferred to be in the range of 0.01-10wt % with respect to the carrier. Although the reaction will stillproceed adequately even if the content of the palladium loading amountis under 0.01 wt %, this presents the risk of lower productivity. Also,although the reaction will still proceed adequately even if the amountis over 10 wt %, the high price of palladium renders this undesirable ineconomic and practical terms. In practice, the range is more preferably0.2-6 wt %. Here, “wt %” refers to the proportion of the weight of the(a) metallic palladium in the catalyst with respect to the weight of thecarrier.

The loading amount of the group (b) compound with respect to the carrierwill also differ depending on the particle size and pore structure ofthe carrier, but it is preferably in the range of 5-200 wt %, and morepreferably in the range of 10-100 wt %, with respect to the carrier.Here, “wt %” refers to the proportion of the weight of the group (b)compound in the catalyst with respect to the weight of the carrier.

The invention (VII) is a non-carrier-held catalyst for production ofacetic acid and ethyl acetate, which is a catalyst used in a process forproduction of acetic acid and ethyl acetate by reaction of ethanol andoxygen that comprises (a) metallic palladium, (b) at least one compoundselected from the group consisting of inorganic acids and salts thereof,and (c) at least one element selected from the group consisting of Group14 elements, Group 15 elements and Group 16 elements of the PeriodicTable (hereinafter may be referred to as group (c) element) or acarrier-held catalyst for production of acetic acid and ethyl acetatewherein these catalyst components are held on a carrier is one of thecatalysts according to the invention (X).

The catalyst of the invention (VII) is the catalyst of the invention(VI) which contains a group (c) element, and it is a ternary catalyst.

The (a) metallic palladium and the group (b) compound used for theinvention (VII) are the same as according to the invention (VI).

The (c) Group 14 elements, Group 15 elements and Group 16 elements ofthe Periodic Table include selenium, tellurium, antimony, tin, bismuthand lead. Selenium, tellurium, tin and bismuth are preferred.

Although the structure of the catalyst has not been fully elucidated,the (a) metallic palladium and the group (b) compound are the same asfor the catalyst of the invention (VI), and the same effect may beexpected as with the catalyst of the invention (VI). The elements andcompounds of these three groups (a), (b) and (c) are believed to existvery close together. The (a) metallic palladium, the group (b) compoundand the group (c) element therefore interact expressing very highactivity and selectivity, i.e. exhibiting low selectivity for carbondioxide and acetaldehyde while exhibiting excellent production activityand selectivity for acetic acid and ethyl acetate.

The compositional ratio of the (a) metallic palladium, the group (b)compound and the group (c) element in the catalyst is preferably (a) 1gram:(b) 0.025-500 grams:(c) 0.005-10 grams, and more preferably (a) 1gram:(b) 0.1-400 grams:(c) 0.01-5 grams. The content of the (a) metallicpalladium in this catalyst is the same as for the catalyst of theinvention (VI).

For loading on a carrier, the carrier is also the same as for thecatalyst of the invention (VI).

The loading amounts of the (a) metallic palladium and the group (b)compound with respect to the carrier are the same as for the catalyst ofthe invention (VI).

The loading amount of the group (c) element with respect to the carrierwill differ depending on the particle size and pore structure of thecarrier, but it is preferably in the range of 0.0001-3.0 wt %, and morepreferably in the range of 0.001-2.0 wt %, with respect to the carrier.Here, “wt %” refers to the proportion of the weight of the group (c)element in the catalyst with respect to the weight of the carrier.

The invention (VIII) is a non-carrier-held catalyst for production ofacetic acid and ethyl acetate, which is a catalyst used in a process forproduction of acetic acid and ethyl acetate by reaction of ethanol andoxygen that comprises (a) metallic palladium, (b) at least one compoundselected from the group consisting of inorganic acids and salts thereof,and (d) at least one element selected from the group consisting of Group6 elements, Group 7 elements, Group 8 elements, Group 9 elements, Group10 elements, Group 11 elements and Group 12 elements of the PeriodicTable (hereinafter may be referred to as group (d) element) or acarrier-held catalyst for production of acetic acid and ethyl acetatewherein these catalyst components are held on a carrier is one of thecatalysts according to the invention (X).

The catalyst of the invention (VIII) is the catalyst of the invention(VI) which contains a group (d) element, and it is a ternary catalyst.

The (a) metallic palladium and the group (b) compound used for theinvention (VIII) are the same as according to the invention (VI).

As the (d) Group 6 elements, Group 7 elements, Group 8 elements, Group 9elements, Group 10 elements, Group 11 elements and Group 12 elements ofthe Periodic Table there may be mentioned chromium, manganese, rhenium,ruthenium, rhodium, iridium, nickel, gold and zinc. Chromium, manganese,gold and zinc are preferred.

Although the structure of the catalyst has not been fully elucidated,the (a) metallic palladium and the group (b) compound are the same asfor the catalyst of the invention (VI), and the same effect may beexpected as with the catalyst of the invention (VI). The elements andcompounds of these three groups (a), (b) and (d) are believed to existvery close together. The (a) metallic palladium, the group (b) compoundand the group (d) element therefore interact expressing very highactivity and selectivity, i.e. exhibiting low selectivity for carbondioxide and acetaldehyde while exhibiting excellent production activityand selectivity for acetic acid and ethyl acetate.

The compositional ratio of the (a) metallic palladium, the group (b)compound and the group (d) element in the catalyst is preferably (a) 1gram:(b) 0.025-500 grams:(d) 0.005-10 grams, and more preferably (a) 1gram:(b) 0.1-400 grams:(d) 0.01-5 grams. The content of the (a) metallicpalladium in this catalyst is the same as for the invention (VI).

For loading on a carrier, the carrier is also the same as for thecatalyst of the invention (VI).

The loading amounts of the (a) metallic palladium and the group (b)compound with respect to the carrier are the same as for the catalyst ofthe invention (VI).

The loading amount of the group (d) element with respect to the carrierwill differ depending on the particle size and pore structure of thecarrier, but it is preferably in the range of 0.0001-3.0 wt %, and morepreferably in the range of 0.001-2.0 wt %, with respect to the carrier.Here, “wt %” refers to the proportion of the weight of the group (d)element in the catalyst, with respect to the weight of the carrier.

The invention (IX) is a non-carrier-held catalyst for production ofacetic acid and ethyl acetate, which is a catalyst used in a process forproduction of acetic acid and ethyl acetate by reaction of ethanol andoxygen that comprises (a) metallic palladium, (b) at least one compoundselected from the group consisting of inorganic acids and salts thereof,(c) at least one element selected from the group consisting of Group 14elements, Group 15 elements and Group 16 elements of the Periodic Table,and (d) at least one element selected from the group consisting of Group6 elements, Group 7 elements, Group 8 elements, Group 9 elements, Group10 elements, Group 11 elements and Group 12 elements of the PeriodicTable on a carrier-held catalyst for production of acetic acid and ethylacetate wherein these catalyst components are held on a carrier is oneof the catalysts according to the invention (X).

The catalyst of the invention (IX) is the catalyst of the invention(VII) which contains a group (d) element, and it is a quaternarycatalyst.

The (a) metallic palladium, the group (b) compound and the group (c)element used for the invention (IX) are the same as for the catalyst ofthe invention (VII). The (d) at least one element selected from thegroup consisting of Group 6 elements, Group 7 elements, Group 8elements, Group 9 elements, Group 10 elements, Group 11 elements andGroup 12 elements of the Periodic Table is the same as according to theinvention (VIII).

Although the structure of the catalyst has not been fully elucidated,the (a) metallic palladium, the group (b) compound and the group (c)element are the same as for the catalyst of the invention (VII), and thesame effect may be expected as by the catalyst of the invention (VII).The elements and compounds of these four groups (a), (b), (c) and (d)are believed to exist very close together. The (a) metallic palladium,the group (b) compound, the group (c) element and the group (d) elementtherefore interact expressing very high activity and selectivity, i.e.exhibiting low selectivity for carbon dioxide and acetaldehyde whileexhibiting excellent production activity and selectivity for acetic acidand ethyl acetate.

The compositional ratio of the (a) metallic palladium, the group (b)compound, the group (c) element and the group (d) element in thecatalyst is preferably (a) 1 gram:(b) 0.025-500 grams:(c) 0.005-10grams:(d) 0.005-10 grams, and more preferably (a) 1 gram:(b) 0.1-400grams:(c) 0.01-5 grams:(d) 0.01-5 grams. The content of the (a) metallicpalladium in this catalyst is the same as for the catalyst of theinvention (VI).

For loading on a carrier, the carrier is also the same as for thecatalyst of the invention (VII).

The loading amounts of the (a) metallic palladium, the group (b)compound and the group (c) element with respect to the carrier are thesame as for the catalyst of the invention (VII).

The loading amount of the group (d) element with respect to the carrierwill differ depending on the particle size and pore structure of thecarrier, but it is preferably in the range of 0.0001-3.0 wt %, and morepreferably in the range of 0.001-2.0 wt %, with respect to the carrier.Here, “wt %” refers to the proportion of the weight of the group (d)element in the catalyst, with respect to the weight of the carrier.

A process for production of a non-carrier-held catalyst of any one ofthe inventions (VI) to (IX) according to the invention (XI) will now beexplained. The process of the invention (XI) is a process for productionof a non-carrier-held catalyst for production of acetic acid and ethylacetate according to any one of the inventions (VI), (VII), (VIII) or(IX).

Production process (1) according to the invention (XI) is a process forproduction of a catalyst according to the invention (VI) that comprisesthe following steps 1 and 2.

Step 1

A step wherein a palladium suspension is obtained.

Step 2

A step wherein (b) at least one compound selected from the groupconsisting of inorganic acids and salts thereof is dissolved orsuspended in the palladium suspension obtained in step 1, and thesolvent is then removed.

Step 1 of production process (1) according to the invention (XI) is astep wherein a palladium suspension is obtained.

In production process (1) according to the invention (XI), there are noparticular restrictions on the palladium compound as the startingmaterial for the metallic palladium. Normally there may be usedcompounds that can be converted to metallic palladium, including halidessuch as palladium chloride, organic acid salts such as palladiumacetate, and also palladium nitrate, palladium oxide, palladium sulfateand sodium tetrachloropalladate, or metallic palladium itself.

The palladium suspension can be obtained by dissolving or suspending themetallic palladium starting compound in an appropriate solvent.

The solvent used here may be water or an inorganic or organic solventsuch as acetone, ethanol or the like, and if necessary an inorganic ororganic acid such as hydrochloric acid, nitric acid or acetic acid maybe dissolved in the solvent that is used. The metallic palladiumstarting compound is preferably one that can be homogeneously dissolvedor suspended by stirring, etc., but it is not particularly restricted.If necessary, the metallic palladium starting compound may also besubjected to reduction treatment for conversion to metallic palladium.

In the case of reduction treatment in step 1, i.e. conversion tometallic palladium of the metallic palladium starting compound that canbe converted to metallic palladium, the method used therefor is notparticularly restricted. Specifically there may be mentioned a methodwhereby the metallic palladium starting compound is reduced to metallicpalladium with an appropriate reducing agent such as hydrazine,formalin, methanol, ethylene, hydrogen or the like. The reductiontreatment may be carried out in either a liquid phase or vapor phasestate. Liquid phase reduction treatment is usually carried out at roomtemperature, but it may also be conducted with heating to a highertemperature, for example, about 30-50° C. Vapor phase reductiontreatment is preferably-carried out with heating to about 100-600° C. inorder to achieve total conversion to metallic palladium.

The palladium suspension can be obtained in this manner.

Step 2 of production process (1) according to the invention (XI) is astep wherein (b) at least one compound selected from the groupconsisting of inorganic acids and salts thereof is dissolved orsuspended in the palladium suspension obtained in step 1, and thesolvent is then removed to obtain a catalyst for production of aceticacid and ethyl acetate.

The group (b) compound which is used for this step is the same as forthe catalyst of the invention (VI).

The method of dissolving or suspending the inorganic acid or saltthereof may be any method that produces homogeneity by stirring, etc.,and it is not particularly restricted. For example, if it will dissolveit may be dissolved directly in the palladium suspension, and if it doesnot dissolve, a method may be employed whereby the inorganic acid orsalt thereof is suspended in an appropriate solvent and the palladiumsuspension is added thereto dropwise.

The method of removing the solvent is not particularly restricted andmay be any well-known method such as heating, pressure reduction, etc.In the case of heating, the temperature is preferably a temperature thatdoes not cause decomposition of the inorganic acid. Particularly in thecase of a heteropoly acid, a temperature of higher than 350° C. canresult in decomposition, and this may impair the activity andselectivity of the catalyst produced by the method.

In step 2 as well, the metallic palladium starting compound may besubjected to reduction treatment if necessary for conversion to metallicpalladium.

In the case of reduction treatment in step 2, i.e. conversion tometallic palladium of the metallic palladium starting compound that canbe converted to metallic palladium, the method used therefor is notparticularly restricted. Specifically there may be mentioned a methodwhereby the metallic palladium starting compound is reduced to metallicpalladium with an appropriate reducing agent such as hydrazine,formalin, methanol, ethylene, hydrogen or the like. The reductiontreatment may be carried out in either a liquid phase or vapor phasestate.

Liquid phase reduction treatment is usually carried out at roomtemperature, but it may also be conducted with heating to a highertemperature, for example, about 30-50° C. Vapor phase reductiontreatment is preferably carried out with heating to about 100-600° C. inorder to achieve total conversion to metallic palladium.

The procedure for conversion to metallic palladium of the metallicpalladium starting compound that can be converted to metallic palladiummay be carried out while the metallic palladium starting compoundcontaining (b) at least one compound selected from the group consistingof inorganic acids and salts thereof is in a suspended solution state,or after separation.

The catalyst of the invention (VI) can be obtained in the mannerdescribed above.

Production process (2) according to the invention (XI) will now beexplained. Production process (2) according to the invention (XI) is aprocess for production of a catalyst according to the invention (VII),and it comprises step 1 and step 2 of production process (1) accordingto the invention (XI), as well as step 3 in which (c) at least oneelement selected from the group consisting of Group 14 elements, Group15 elements and Group 16 elements of the Periodic Table is added ineither or both of these steps.

The starting compound for the (a) metallic palladium used in step 1 ofthis process, and the method for its dissolution or suspension, are thesame as in step 1 of production process (1) for the catalyst of theinvention (VI), according to the invention (XI).

The starting material that gives the group (c) element is notparticularly restricted, and it may be the element itself or a halide,nitrate, acetate, phosphate, sulfate or oxide containing the element, oreven a complex with an organic molecule such as acetyl-acetonato ornitrile as the ligand.

Specifically there may be mentioned chlorides such as selenium chloride,tellurium chloride, antimony chloride, tin chloride, bismuth chloride,lead chloride, etc.; nitrates such as antimony nitrate, tin nitrate,bismuth nitrate, lead nitrate, etc.; acetates such as tin acetate,bismuth acetate, lead acetate, etc.; and selenium oxide, selenic acid(H₂SeO₄) and its salts, selenious acid (H₂SeO₃) and its salts, telluriumoxide, telluric acid (H₆TeO₆) and its salts, tellurous acid (H₂TeO₃) andits salts, metallic tellurium, potassium antimonate and the like, butthere is no limitation to these.

The method of dissolving or suspending the starting compound for thegroup (c) element, when a group (c) element is added in step 1, may beany method that produces homogeneity by stirring, etc. with the metallicpalladium starting compound, and it is not particularly restricted. Forexample, if it will dissolve it may be dissolved directly together withthe starting compound of the metallic palladium, and if it does notdissolve, a method may be employed whereby the starting compound for thegroup (c) element is suspended in an appropriate solvent and theresulting solution is added dropwise to a solution in which the metallicpalladium starting compound has been dissolved or suspended.

The solvent used here may be water or an inorganic or organic solventsuch as acetone, ethanol or the like, and, if necessary, an inorganicacid or organic acid such as hydrochloric acid, nitric acid or aceticacid may be dissolved in the solvent that is used. The starting compoundfor the group (c) element is preferably one that can be homogeneouslydissolved or suspended by stirring, etc., but it is not particularlyrestricted.

When a metallic palladium starting compound that can be converted tometallic palladium is converted to metallic palladium in step 1, themethod therefor, i.e. the reduction treatment method, is the same as instep 1 of production process (1) according to the invention (XI).

The palladium suspension may be obtained in the manner described above.

The group (b) compound used for step 2 is the same as for the catalystof the invention (VI), and the method of dissolving or suspending thegroup (b) compound and the method of removing the solvent are the sameas in step 2 of production process (1) according to the invention (XI).

When a group (c) element is added in step 2, the starting compound forthe element and the method of dissolving or suspending the startingcompound for the group (c) element may be the same as in step 1 ofproduction process (2) according to the invention (XI).

There are no particular restrictions on the order of adding the group(b) compound and the group (c) element to the palladium suspension, andtwo or more may be added simultaneously or in any desired order. Thatis, a group (b) compound and a group (c) element may be addedsimultaneously, or a group (c) element may be added and separated priorto adding the group (b) compound.

When a metallic palladium starting compound that can be converted tometallic palladium is converted to metallic palladium in step 2, themethod therefor, i.e. the reduction treatment method, is the same as instep 2 of production process (1) according to the invention (XI).

The catalyst of the invention (VII) can be obtained in the mannerdescribed above.

Production process (3) according to the invention (XI) will now beexplained. Production process (3) according to the invention (XI) is aprocess for production of a catalyst according to the invention (VIII),and it comprises step 1 and step 2 of production process (1) accordingto the invention (XI), as well as step 3 in which (d) at least oneelement selected from the group consisting of Group 6 elements, Group 7elements, Group 8 elements, Group 9 elements, Group 10 elements, Group11 elements and Group 12 elements of the Periodic Table is added ineither or both of these steps.

The starting compound for the (a) metallic palladium used in step 1 ofthis process, and the method for its dissolution or suspension, are thesame as in step 1 of production process (1) according to the invention(XI).

The starting material that gives the group (d) element is notparticularly restricted, and it may be the element itself or a halide,nitrate, acetate, phosphate, sulfate or oxide containing the element, oreven a complex with an organic molecule such as acetylacetonato ornitrile as the ligand. Specifically there may be mentioned chloridessuch as chromium chloride, manganese chloride, rhenium chloride,ruthenium chloride, rhodium chloride, iridium chloride, nickel chloride,tetrachloro aurate and its salts, zinc chloride and its-salts, etc.;nitrates such as chromium nitrate, manganese nitrate, nickel nitrate,iridium nitrate, zinc nitrate, etc.; acetates such as chromium acetate,manganese acetate, rhenium acetate, ruthenium acetate, iridium acetate,nickel acetate, zinc acetate, and the like, but there is no limitationto these.

The method of dissolving or suspending the starting compound for thegroup (d) element, when it is added in step 1, may be any method thatproduces homogeneity by stirring, etc. with the metallic palladiumstarting compound, and it is not particularly restricted. For example,if it will dissolve it may be dissolved directly together with thestarting compound of the metallic palladium, and if it does notdissolve, a method may be employed whereby the starting compound for thegroup (d) element is suspended in an appropriate solvent and theresulting solution is added dropwise to a solution in which the metallicpalladium starting compound has been dissolved or suspended.

The solvent used here may be water or an inorganic or organic solventsuch as acetone, ethanol or the like, and, if necessary, an inorganic.acid or organic acid such as hydrochloric acid, nitric acid or aceticacid may be dissolved in the solvent that is used. The starting compoundfor the group (d) element is preferably one that can be homogeneouslydissolved or suspended by stirring, etc., but it is not particularlyrestricted.

When a metallic palladium starting compound that can be converted tometallic palladium is converted to metallic palladium in step 1, themethod therefor, i.e. the reduction treatment method, is the same as instep 1 of production process (1) according to the invention (XI).

The palladium suspension may be obtained in the manner described above.

The group (b) compound used for step 2 is the same as for the catalystof the invention (VI), and the method of dissolving or suspending thegroup (b) compound and the method of removing the solvent are the sameas in step 2 of production process (1) for the catalyst of the invention(VI), according to the invention (XI).

When a group (d) element is added in step 2, the starting compound forthe element and the method of dissolving or suspending the startingcompound for the group (d) element may be the same as in step 1 ofproduction process (3).

There are no particular restrictions on the order of adding the group(b) compound and the group (d) element to the palladium suspension, andtwo or more may be added simultaneously or in any desired order. Thatis, a group (b) compound and a group (d) element may be addedsimultaneously, or a group (d) element may be added and separated priorto adding the group (b) compound.

When a metallic palladium starting compound that can be converted tometallic palladium is converted to metallic palladium in step 2, themethod therefor, i.e. the reduction treatment method, is the same as instep 2 of production process (1) according to the invention (XI).

The catalyst of the invention (VIII) can be obtained in the mannerdescribed above.

Production process (4) according to the invention (XI) will now beexplained. Production process (4) according to the invention (XI) is aprocess for production of a catalyst according to the invention (IX),and it comprises step 1 and step 2 of production process (1) accordingto the invention (XI), as well as step 3 in which (c) at least oneelement selected from the group consisting of Group 14 elements, Group15 elements and Group 16 elements of the Periodic Table and (d) at leastone element selected from the group consisting of Group 6 elements,Group 7 elements, Group 8 elements, Group 9 elements, Group 10 elements,Group 11 elements and Group 12 elements of the Periodic Table, are addedin either or both of these steps.

The starting compound for the (a) metallic palladium used in step 1 ofthis process, and the method for its dissolution or suspension, are thesame as in step 1 of production process (I) according to the invention(XI).

The starting material that gives the group (c) element, and the methodfor its dissolution or suspension, are the same as in step 1 ofproduction process (2) according to the invention (XI).

The starting material that gives the group (d) element, and the methodfor its dissolution or suspension, are the same as in step 1 ofproduction process (3) for a catalyst according to the invention (XI).

When a metallic palladium starting compound that can be converted tometallic palladium is converted to metallic palladium in step 1, themethod therefor, i.e. the reduction treatment method, is the same as instep 1 of production process (1) according to the invention (XI).

The palladium suspension may be obtained in the manner described above.

The group (b) compound used for step 2 is the same as for the catalystof the invention (VI), and the method of dissolving or suspending thegroup (b) compound and the method of removing the solvent are the sameas in step 2 of production process (1) for the catalyst of the invention(VI), according to the invention (XI).

When a group (c) element is added in step 2, the starting compound forthe element and the method of dissolving or suspending the startingcompound for the group (c) element may be the same as in step 1 ofproduction process (2) for the catalyst of the invention (VII),according to the invention (XI).

When a group (d) element is added in step 2, the starting compound forthe element and the method of dissolving or suspending the startingcompound for the group (d) element may be the same as in step 1 ofproduction process (3) for the catalyst of the invention (VIII),according to the invention (XI).

There are no particular restrictions on the order of adding the group(b) compound and/or the group (c) element and/or the group (d) elementto the palladium suspension, and three or more may be addedsimultaneously or in any desired order. That is, a group (b) compound, agroup (c) element and a group (d) element may be added simultaneously,or a group (b) compound and a group (c) element may be addedsimultaneously and separated, and then another suspension containing agroup (b) compound and a group (c) element may be prepared and a group(d) element added thereto.

When a metallic palladium starting compound that can be converted tometallic palladium is converted to metallic palladium in step 2, themethod therefor, i.e. the reduction treatment method, is the same as instep 2 of production process (1) according to the invention (XI).

The catalyst of the invention (IX) can be obtained in the mannerdescribed above.

A process for production of a carrier-held catalyst of the invention (X)according to the invention (XII) will now be explained. The process ofthe invention (XII) is a process for production of a carrier-heldcatalyst for production of acetic acid and ethyl acetate according tothe invention (X).

Production process (1) for a carrier-held catalyst of the invention (X)according to the invention (XII) comprises the following steps 1 and 2.

Step 1

A step wherein (a) metallic palladium is loaded on a carrier to obtain ametallic palladium-loaded catalyst.

Step 2

A step wherein (b) at least one compound selected from the groupconsisting of inorganic acids and salts thereof is loaded on themetallic palladium-loaded catalyst obtained in step 1 to obtain acatalyst for production of acetic acid and ethyl acetate.

Step 1 of production process (1) according to the invention (XII) is astep wherein metallic palladium is loaded on a carrier to obtain ametallic palladium-loaded catalyst.

The metallic palladium starting compound used in step 1 is the same asin step 1 of production process (1) according to the invention (XI).

There are no particular restrictions on the method of loading themetallic palladium, or the metallic palladium starting compound-that canbe converted to metallic palladium, on the carrier, and the loading maybe accomplished by any method. For example, for loading of a metallicpalladium starting compound that can be converted to metallic palladium,the loading on the carrier may be accomplishing by dissolving orsuspending the metallic palladium starting compound in an appropriatesolvent such as water or acetone, an inorganic or organic acid such ashydrochloric acid, nitric acid, acetic acid, etc., or a mixture thereof,and then loading the solution onto the carrier and drying it. For theloading process there may be mentioned means such as the impregnationmethod, evaporation to dry hardness method, kneading method and spraymethod, but there is no limitation to these.

When a metallic palladium starting compound that can be converted tometallic palladium is loaded, the method of subsequently converting themetallic palladium starting compound to metallic palladium, i.e. thereduction treatment method, is not particularly restricted. Thereduction treatment may be carried out in either a liquid phase or vaporphase state, and the conditions are not particularly restricted so longas they are common reducing conditions. Liquid phase reduction treatmentis usually carried out at room temperature, but it may also be conductedwith heating to a higher temperature, for example, about 30-50° C. Vaporphase reduction treatment is preferably carried out with heating of themetallic palladium starting compound-loaded carrier to about 100-600° C.in order to achieve total conversion to metallic palladium.

Specifically there may be mentioned a method whereby the metallicpalladium starting compound is reduced to metallic palladium using anappropriate reducing agent such as hydrazine, formalin, hydrogen,methanol, ethylene or the like, either directly or after treatment withan aqueous solution of sodium hydroxide, potassium hydroxide, bariumhydroxide, sodium metasilicate, etc. to convert the metallic palladiumstarting compound to an oxide, hydroxide, or the like.

The procedure for conversion to metallic palladium of the metallicpalladium starting compound that can be converted to metallic palladiummay be carried out after separating the catalyst holding the metallicpalladium starting compound, or it may be carried out immediatelyfollowing the loading procedure. If conditions permit, it is preferablycarried out immediately following the loading procedure, withoutseparation.

If desired, the metallic palladium-loaded catalyst may then be filteredby a common method and then washed and dried to remove out anyreaction-inhibiting substances for the catalytic reaction, such ashalides or alkali salts of sodium, etc.

The metallic palladium-loaded catalyst can be obtained in the mannerdescribed above.

Step 2 of production process (1) according to the invention (XII) is astep wherein a catalyst of the invention (X) is obtained by loading (b)at least one compound selected from the group consisting of inorganicacids and salts thereof on the metallic palladium-loaded catalystobtained in step 1.

In step 2, the group (b) compound is the same as for the catalyst of theinvention (VI). There are no particular restrictions on the method ofloading the group (b) compound, and the loading may be accomplished byany publicly known method. Specifically there may be mentioned suchmeans as the impregnation method, spray method, evaporation to dryhardness method, kneading method and adsorption method, but there is nolimitation to these. The solvent used for impregnation may be any onewhich can dissolve the inorganic acid, and water, organic solvents andtheir mixtures may be used. Water, alcohol and the like are preferablyused.

A catalyst of the invention (X) can be obtained in this manner.

Production process (2) for a carrier-held catalyst of the invention (X)according to the invention (XII) comprises addition of (c) at least oneelement selected from the group consisting of Group 14 elements, Group15 elements and Group 16 elements of the Periodic Table, in either orboth of steps 1 and 2 of production process (1) according to theinvention (XII).

The starting compound for the (a) metallic palladium used in step 1 ofproduction process (2), and the method for its loading and conversion tometallic palladium, are the same as in step 1 of production process (1)according to the invention (XII).

When a group (c) element is added in step 1, the starting compound forthe group (c) element is the same as in step 1 of production process (2)according to the invention (XI).

There are no particular restrictions on the method of loading thestarting compound for the group (c) element on the carrier, and theloading may be accomplished by any method. For example, the startingcompound for the group (c) element may be dissolved in an appropriatesolvent such as water or acetone, in an inorganic acid or organic acidsuch as hydrochloric acid, nitric acid, acetic acid, or the like, andthen impregnated into the carrier and dried, as the method of loadingonto the carrier.

The loading method may be any of such means as the impregnation method,evaporation to dry hardness method, kneading method, spray method, orthe like, but there is no limitation to these.

The loading of the starting compound for the (a) metallic palladium onthe carrier and the loading of the starting compound for the group (c)element on the carrier may be carried out in any order. That is, bothloadings may be carried out simultaneously, or one before the other.Preferred and most common is simultaneous loading on the carrier of thestarting compound for the group (c) element and the starting compoundfor the (a) metallic palladium on the carrier.

If desired, the metallic palladium-loaded catalyst may then be filteredby a common method and then washed and dried to remove out anyreaction-inhibiting substances for the catalytic reaction, such ashalides or alkali salts of sodium, etc.

The metallic palladium-loaded catalyst can be obtained in the mannerdescribed above.

Step 2 of production process (2) is a step whereby a catalyst of theinvention (X) is obtained by loading (b) at least one compound selectedfrom the group consisting of inorganic acids and salts thereof and/or(c) at least one element selected from the group consisting of Group 14elements, Group 15 elements and Group 16 elements of the Periodic Tableon the metallic palladium-loaded catalyst obtained in step 1.

In step 2, the group (b) compound and the method for its loading are thesame as in step 2 of production process (1) according to the invention(XII).

When a group (c) element is loaded in step 2, the starting compound forthe group (c) element and the method of its loading are the same as instep 1 of production process (2).

The loading of the group (b) compound on the metallic palladium-loadedcatalyst and the loading of the starting compound for the group (c)element on the metallic palladium-loaded catalyst may be carried out inany order. That is, both loadings may be carried out simultaneously, orone before the other.

A catalyst of the invention (X) can be obtained in the manner describedabove.

Production process (3) for a carrier-held catalyst of the invention (X)according to the invention (XII) comprises a step of adding (d) at leastone element selected from the group consisting of Group 6 elements,Group 7 elements, Group 8 elements, Group 9 elements, Group 10 elements,Group 11 elements and Group 12 elements of the Periodic Table in eitheror both step 1 and step 2 of production process (1) according to theinvention (XII).

The starting compound for the (a) metallic palladium used in step 1 ofproduction process (3), and the method for its loading and conversion tometallic palladium, are the same as in step 1 of production process (1)according to the invention (XII).

When a group (d) element is added in step 1, the starting compound forthe group (d) element is the same as in step 1 of production process (3)according to the invention (XI).

There are no particular restrictions on the method of loading thestarting compound for the group (d) element on the carrier, and anymethod may be employed. For example, the starting compound for the group(d) element may be dissolved in an appropriate solvent such as water oracetone, in an inorganic acid or organic acid such as hydrochloric acid,nitric acid, acetic acid, or the like, and then impregnated into thecarrier and dried, as the method of loading onto the carrier.

The loading method may be any of such means as the impregnation method,evaporation to dry hardness method, kneading method, spray method, orthe like, but there is no limitation to these.

The loading of the starting compound for the (a) metallic palladium onthe carrier and the loading of the starting compound for the group (d)element on the carrier may be carried out in any order. That is, bothloadings may be carried out simultaneously, or one before the other.Preferred and most common is simultaneous loading on the carrier of thestarting compound for the group (d) element and the starting compoundfor the (a) metallic palladium on the carrier.

If desired, the metallic palladium-loaded catalyst may then be filteredby a common method and then washed and dried to remove out anyreaction-inhibiting substances for the catalytic reaction, such ashalides or alkali salts of sodium, etc.

The metallic palladium-loaded catalyst can be obtained in the mannerdescribed above.

Step 2 of production process (3) is a process whereby a catalyst of theinvention (X) is obtained by loading (b) at least one compound selectedfrom the group consisting of inorganic acids and salts thereof and/or(d) at least one element selected from the group consisting of Group 6elements, Group 7 elements, Group 8 elements, Group 9 elements, Group 10elements, Group 11 elements and Group 12 elements of the Periodic Tableon the metallic palladium-loaded catalyst obtained in step 1.

In step 2, the group (b) compound and the method for its loading are thesame as in step 2 of production process (1) according to the invention(XII).

When a group (d) element is loaded in step 2, the starting compound forthe group (d) element and the method of its loading are the same as instep 1 of production process (3).

The loading of the group (b) compound on the metallic palladium-loadedcatalyst and the loading of the starting compound for the group (d)element on the metallic palladium-loaded catalyst may be carried out inany order. That is, both loadings may be carried out simultaneously, orone before the other.

A catalyst of the invention (X) can be obtained in the manner describedabove.

Production process (4) for a carrier-held catalyst of the invention (X)according to the invention (XII) is a production process used to obtaina catalyst of the invention (IV). The catalyst of the invention (IV)allows production by adding (c) at least one element selected from thegroup consisting of Group 14 elements, Group 15 elements and Group 16elements of the Periodic Table and (d) at least one element selectedfrom the group consisting of Group 6 elements, Group 7 elements, Group 8elements, Group 9 elements, Group 10 elements, Group 11 elements andGroup 12 elements of the Periodic Table in either or both step 1 andstep 2 of production process (1) according to the invention (XII).

In production process (4), the starting compound for the (a) metallicpalladium used in step 1, and the method for its loading and conversionto metallic palladium, are the same as in step 1 of production process(1) according to the invention (XII).

When a group (c) element is added in step 1, the starting compound forthe group (c) element and the method for its loading are the same as instep 1 of production process (2) according to the invention (XII).

When a group (d) element is added, the starting compound for the group(d) element and the method for its loading are the same as in step 1 ofproduction process (3) according to the invention (XII).

The loading of the starting compound for the (a) metallic palladium onthe carrier and the loading of the starting compound for the group (c)element and/or the starting compound for the group (d) element on thecarrier may be carried out in any order. That is, all three loadings maybe carried out simultaneously, or any one before the others. Preferredand most common is loading on the carrier of the starting compound forthe group (c) element and the starting compound for the group (d)element simultaneously with the starting compound for the (a) metallicpalladium.

If desired, the metallic palladium-loaded catalyst may then be filteredby a common method and then washed and dried to remove out anyreaction-inhibiting substances for the catalytic reaction, such ashalides or alkali salts of sodium, etc.

The metallic palladium-loaded catalyst can be obtained in the mannerdescribed above.

Step 2 of production process (4) is a process whereby a catalyst of theinvention (X) is obtained by loading (b) at least one compound selectedfrom the group consisting of inorganic acids and salts thereof and/or(c) at least one element selected from the group consisting of Group 14elements, Group 15 elements and Group 16 elements of the Periodic Tableand/or (d) at least one element selected from the group consisting ofGroup 6 elements, Group 7 elements, Group 8 elements, Group 9 elements,Group 10 elements, Group 11 elements and Group 12 elements of thePeriodic Table on the metallic palladium-loaded catalyst obtained instep 1.

In step 2, the group (b) compound and the method for its loading are thesame as in step 2 of production process (1) according to the invention(XII).

When a group (c) element is loaded in step 2, the starting compound forthe group (c) element and the method for its loading are the same as instep 1 of production process (2) according to the invention (XII).

When a group (d) element is loaded in step 2, the starting compound forthe group (d) element and the method for its loading are the same as instep 1 of production process (3) according to the invention (XII).

In step 2, the loading of the group (b) compound on the metallicpalladium-loaded catalyst and/or the loading of the starting compoundfor the group (c) element and/or the starting compound for the group (d)element on the metallic palladium-loaded catalyst may be carried out inany order. That is, the loadings may be carried out simultaneously, orany one before the others.

A catalyst of the invention (X) can be obtained in the manner describedabove.

The process for production of acetic acid and ethyl acetate according tothe invention (XIII) will now be explained. The invention (XIII) is aprocess for production of acetic acid and ethyl acetate from ethanol andoxygen using a catalyst according to any one of the inventions (VI) to(X).

The reaction process is not particularly restricted so long as it allowsthe catalyst of the invention to react ethanol with oxygen, and it maybe any of a variety of processes including a batch process, semi-batchprocess, semi-continuous process, continuous flow process or acombination thereof, for a vapor phase reaction and/or liquid phasereaction.

The ethanol starting material may be supplied in liquid form, or it maybe supplied in vapor form. That is, the reaction process may be, forexample, a semi-continuous process whereby the catalyst of the inventionis suspended in liquid ethanol and/or an ethanol solution and oxygen ispassed through, or a continuous flow process whereby ethanol and oxygengas are passed through the catalyst. A vapor phase continuous flowprocess if preferred from the standpoint of separation of the catalyst,starting materials and products, and the standpoint of productivity.More preferred, and advantageous in practical terms, is to employ afixed bed having corrosion-resistant reaction tubes packed with thecatalyst of the invention, for a vapor phase reaction in which theethanol and oxygen are passed through.

A vapor phase reaction and liquid phase reaction used for production ofacetic acid and ethyl acetate according to the invention (XIII) will nowbe explained.

A vapor phase reaction will be explained first.

There are no particular restrictions on the reaction temperature for thereaction of ethanol and oxygen in a vapor phase according to the aceticacid and ethyl acetate production method of the invention (XIII), but itis preferably 100-250° C. If the reaction temperature is below 100° C.the reaction rate may be insufficient, while if it is above 250° C. agreater number of secondary reactions will tend to occur. More preferredin practical terms is the range of 110-230° C.

In terms of the equipment, it is advantageous in practice for thereaction pressure to be from 0.0 to 3.0 MPa (gauge pressure), and morepreferably in the range of 0.1 to 1.5 MPa (gauge pressure).

In the case of a flow-type reaction, the gas supplied to the reactionsystem comprises ethanol and oxygen, and if necessary nitrogen, carbondioxide, a rare gas or the like may also be used as a diluent. Theethanol is supplied to the reaction system in an amount corresponding toa proportion of 0.1-50% by volume, and especially 0.5-40% by volume, andthe oxygen in an amount corresponding to a proportion of 1-15% byvolume, and especially 2-10% by volume, with respect to the total amountof supply gas. Here, a high concentration of ethanol in the supply gaswill result in greater production of ethyl acetate, while a lowerconcentration will tend to result in higher selectivity for acetic acid.An ethanol concentration exceeding 50% by volume will tend to increasethe number of secondary reactions, while a concentration of under 0.1%by volume will tend to lower the productivity.

The presence of water in the reaction system will provide a notableeffect of improved acetic acid and ethyl acetate production activity andselectivity, as well as prolonged activity of the catalyst in thereaction system. It is suitable for water vapor to be included in thereaction gas at 0.1-50% by volume. If the water vapor in the reactiongas is present at less than 0.1% by volume the catalyst may tend toundergo deterioration more readily, and if it is present at greater than50% by volume, the steam unit requirement may be poorer. In practicalterms, the range is preferably 0.5-40% by volume.

When carrying out the process of the invention (XIII) by this gas phasereaction it is advantageous to use a high purity ethanol startingmaterial, but there is no problem with mixing a small amount of a lowersaturated hydrocarbon such as methane, ethane or propane, oracetaldehyde, diethyl ether, ethylene or the like. In particular,acetaldehyde, diethyl ether and ethylene that are trace by-products ofthis reaction can be converted to acetic acid and/or ethyl acetate by acatalyst of the invention. The oxygen can also be in a form such as air,diluted with an inert gas such as nitrogen, carbon dioxide gas or thelike, but when the reaction gas is circulated it is generally moreadvantageous to use oxygen at a high concentration, preferably 99% orgreater. The reaction mixture gas is preferably passed through thecatalyst at a space velocity (SV) in the range of 500-15,000 hr⁻¹, andespecially 1000-10,000 hr⁻¹, in a standard state.

Next, a liquid phase reaction will be explained.

There are no particular restrictions on the reaction temperature for thereaction of ethanol and oxygen in a liquid phase according to the aceticacid and ethyl acetate production method of the invention (XIII), but itis preferably 0-200° C. If the reaction temperature is below 0° C. thereaction rate may be insufficient, while if it is above 200° C. agreater-number of secondary reactions will tend to occur. More preferredin practical terms is the range of 20-110° C.

In terms of the equipment, it is advantageous in practice for thereaction pressure to be from 0.0 to 3.0 MPa (gauge pressure), and morepreferably in the range of 0.1 to 1.5 MPa (gauge pressure).

The ethanol and/or oxygen starting materials may be present in thecatalyst beforehand, or they may be added at an appropriate point duringthe reaction. When they are supplied to the reaction system, they may bein gaseous and/or liquid form. The starting material supplied to thereaction system comprises ethanol and oxygen, and if necessary nitrogen,carbon dioxide or a diluting gas may also be used.

The presence of water in the reaction system will provide a notableeffect of improved acetic acid and ethyl acetate production activity andselectivity, as well as prolonged activity of the catalyst in thereaction system. The proportion of water and ethanol in the reactionsystem is not particularly restricted. The proportion of water andethanol may even be changed during the reaction, or an appropriateamount of water may be added to keep a constant proportion. If desired,a basic component such as sodium hydroxide may be added to increase thereaction rate.

When carrying out the invention (XIII) by this liquid phase reaction itis advantageous to use a high purity ethanol starting material, butthere is no problem with mixing a small amount of a lower saturatedhydrocarbon such as methane, ethane or propane, or acetaldehyde, diethylether, ethylene or the like. In particular, acetaldehyde, diethyl etherand ethylene that are trace by-products of this reaction can beconverted to acetic acid and/or ethyl acetate by a catalyst of theinvention. The oxygen can also be in a form such as air, diluted with aninert gas such as nitrogen, carbon dioxide gas or the like, but when thereaction gas is circulated it is generally more advantageous to useoxygen at a high concentration, preferably 99% or greater.

Production of acetic acid and ethyl acetate according to the invention(XIII) in this manner allows acetic acid and ethyl acetate to beobtained with high activity and high selectivity from ethanol andoxygen. The acetic acid and ethyl acetate obtained may be separated andpurified by common methods, to the desired degree of purity. Whenunreacted starting materials and by-products of acetaldehyde, diethylether and ethylene remain, those unreacted starting materials andby-products of acetaldehyde, diethyl ether and ethylene can be recoveredand recycled into the reaction system for use.

When either acetic acid or ethyl acetate is required for industrial use,it may be separated and removed after the reaction to obtain the desiredsubstance, and the other product returned to the reaction system. Forexample, if ethyl acetate is required, the desired ethyl acetate may beseparated and recovered after the reaction and the acetic acid returnedto the reaction system, to obtain additional ethyl acetate from aceticacid and ethanol.

When necessary, the catalyst used may be regenerated at an appropriatepoint or separated for repeated used.

The present invention will now be explained in greater detail by way ofthe following examples, which are only generally illustrative of theinvention and are not intended to restrict it in any way.

All of the carriers used in the following examples were dried in air at110° C. for 4 hours, as pretreatment. The water used in the examples wasdeionized water.

EXAMPLE 1

A silica carrier [KA-1, particle size: 5 mmφ, product of Züd-chemie AG](69 g) was added to an aqueous solution (45 ml) of sodiumtetrachloropalladate [Na₂PdCl₄, product of Tanaka Kikinzoku] (1.90 g)and telluric acid [H₆TeO₆, product of Kanto Chemical Co.] (0.13 g), toabsorb the entire amount. This was then added to an aqueous solution(100 ml) of sodium metasilicate nonahydrate [Na₂SiO₃•9H₂O, product ofWako Junyaku] (5.5 g), and the mixture was allowed to stand at roomtemperature for 20 hours. After then adding hydrazine monohydrate[N₂H₄•H₂O, product of Wako Junyaku] (5 g) thereto and gently stirring,the mixture was allowed to stand at room temperature for 4 hours forreduction to metallic palladium. After filtering the catalyst andperforming decantation, it was transferred to a glass column equippedwith a stopcock and purified water was passed through for 40 hours at arate of about 1.5 liters per hour for washing. This was then dried for 4hours under an air stream at 110° C. to obtain acetic acid productioncatalyst 1.

EXAMPLE 2

Acetic acid production catalyst 2 was obtained by the same procedure asExample 1, except that lead acetate trihydrate [(CH₃COO)₂Pb, product ofWako Junyaku] (0.74 g) was used instead of the telluric acid in Example1.

EXAMPLE 3

A silica carrier [KA-1, particle size: 5 mmφ, product of Züd-chemie AG](69 g) was added to an aqueous solution (45 ml) of sodiumtetrachloropalladate (1.90 g), to absorb the entire amount. This wasthen added to an aqueous solution (100 ml) of sodium metasilicatenonahydrate (5.5 g), and the mixture was allowed to stand at roomtemperature for 20 hours. After then adding hydrazine monohydrate (5 g)thereto and gently stirring, the mixture was allowed to stand at roomtemperature for 4 hours for reduction to metallic palladium. Afterfiltering the catalyst and performing decantation, it was transferred toa glass column equipped with a stopcock and purified water was passedthrough for 40 hours at a rate of about 1.5 liters per hour for washing.This was then dried for 4 hours under an air stream at 110° C. to obtaina metallic palladium-loaded catalyst.

This metallic palladium-loaded catalyst was then added to an aqueoussolution (45 ml) of sodium tellurite [Na₂TeO₃, product of Wako Junyaku](0.12 g) to absorb the entire amount. This was then dried for 4 hoursunder an air stream at 110° C. to obtain acetic acid production catalyst3.

EXAMPLE 4

Acetic acid production catalyst 4 was obtained by the same procedure asExample 3, except that an acetic acid solution of bismuth nitratepentahydrate [Bi(NO₃)₂•5H₂O, product of Wako Junyaku] (0.37 g) was usedinstead of the sodium tellurite in Example 3.

EXAMPLE 5

Acetic acid production catalyst 5 was obtained by the same procedure asExample 3, except that an acetic acid solution of tin acetate[CH₃(COO)₂Sn, product of Wako Junyaku] (0.26 g) was used instead of thesodium tellurite in Example 3.

EXAMPLE 6

A silica carrier [CARiACT, Q-10, product of Fuji Silicia Chemical Co.](57 g) was added to an aqueous solution (56 ml) of sodiumtetrachloropalladate (1.90 g), to absorb the entire amount. This wasthen added to an aqueous solution (100 ml) of sodium metasilicatenonahydrate (6.0 g), and the mixture was allowed to stand at roomtemperature for 20 hours. After then adding hydrazine monohydrate (5 g)thereto and gently stirring, the mixture was allowed to stand at roomtemperature for 4 hours for reduction to metallic palladium. Afterfiltering the catalyst and performing decantation, it was transferred toa glass column equipped with a stopcock and purified water was passedthrough for 40 hours at a rate of about 1.5 liters per hour for washing.This was then dried for 4 hours under an air stream at 110° C. to obtaina metallic palladium-loaded catalyst.

This metallic palladium-loaded catalyst was then added to an aqueoussolution (55 ml) of sodium tellurite (0.12 g) to absorb the entireamount. This was then dried for 4 hours under an air stream at 110° C.to obtain acetic acid production catalyst 6.

EXAMPLE 7

A titania carrier [CS-300S-46, particle size: 3-5 mmφ, product of SakaiChemical Industries] (107 g) was added to an aqueous solution (42 ml) ofsodium tetrachloropalladate (1.90 g), to absorb the entire amount. Thiswas then added to an aqueous solution (100 ml) of sodium metasilicatenonahydrate (6.0 g), and the mixture was allowed to stand at roomtemperature for 20 hours. After then adding hydrazine monohydrate (5 g)thereto and gently stirring, the mixture was allowed to stand at roomtemperature for 4 hours for reduction to metallic palladium. Afterfiltering the catalyst and performing decantation, it was transferred toa glass column equipped with a stopcock and purified water was passedthrough for 40 hours at a rate of about 1.5 liters per hour for washing.This was then dried for 4 hours under an air stream at 110° C. to obtaina metallic palladium-loaded catalyst.

This metallic palladium-loaded catalyst was then added to an aqueoussolution (42 ml) of sodium tellurite (0.12 g) to absorb the entireamount. This was then dried for 4 hours under an air stream at 110° C.to obtain acetic acid production catalyst 7.

EXAMPLE 8

A silica carrier [KA-1, particle size: 5 mmφ, product of Züd-chemie AG](69 g) was added to an aqueous solution (45 ml) of sodiumtetrachloropalladate (1.90 g) and tetrachloro aurate tetrahydrate[H₄AuCl₄•4H₂O, product of Tanaka Kikinzoku] (0.50 g), to absorb theentire amount. This was then added to an aqueous solution (100 ml) ofsodium metasilicate nonahydrate (6.9 g), and the mixture was allowed tostand at room temperature for 20 hours. After then adding hydrazinemonohydrate (6.5 g) thereto and gently stirring, the mixture was allowedto stand at room temperature for 4 hours for reduction to metallicpalladium. After filtering the catalyst and performing decantation, itwas transferred to a glass column equipped with a stopcock and purifiedwater was passed through for 40 hours at a rate of about 1.5 liters perhour for washing. This was then dried for 4 hours under an air stream at110° C. to obtain acetic acid production catalyst 8.

EXAMPLE 9

Acetic acid production catalyst 9 was obtained by the same procedure asExample 8, except that zinc chloride [ZnCl₂, product of Wako Junyaku](0.08 g) was used instead of the tetrachloro aurate tetrahydrate inExample 8.

EXAMPLE 10

Acetic acid production catalyst 10 was obtained by the same procedure asExample 8, except that chromium chloride hexahydrate [CrCl₃•6H₂O,product of Wako Junyaku] (0.22 g) was used instead of the tetrachloroaurate tetrahydrate in Example 8.

EXAMPLE 11

Acetic acid production catalyst 11 was obtained by the same procedure asExample 8, except that manganese chloride tetrahydrate [MnCl₂•4H₂O,product of Wako Junyaku] (0.23 g) was used instead of the tetrachloroaurate tetrahydrate in Example 8.

EXAMPLE 12

A silica carrier [KA-1, particle size: 5 mmφ, product of Züd-chemie AG](69 g) was added to an aqueous solution (45 ml) of sodiumtetrachloropalladate (1.90 g) and tetrachloro aurate tetrahydrate (0.50g), to absorb the entire amount. This was then added to an aqueoussolution (100 ml) of sodium metasilicate nonahydrate (6.9 g), and themixture was allowed to stand at room temperature for 20 hours. Afterthen adding hydrazine monohydrate (6.5 g) thereto and gently stirring,the mixture was allowed to stand at room temperature for 4 hours forreduction to metallic palladium. After filtering the catalyst andperforming decantation, it was transferred to a glass column equippedwith a stopcock and purified water was passed through for 40 hours at arate of about 1.5 liters per hour for washing. This was then dried for 4hours under an air stream at 110° C. to obtain a metallicpalladium-loaded catalyst containing gold.

This metallic palladium-loaded catalyst was then added to an aqueoussolution (45 ml) of sodium tellurite (0.12 g), to absorb the entireamount. It was then dried for 4 hours under an air stream at 110° C. toobtain acetic acid production catalyst 12.

EXAMPLE 13

Acetic acid production catalyst 13 was obtained by the same procedure asExample 12, except that zinc chloride (0.08 g) was used instead of thetetrachloro aurate in Example 12.

EXAMPLE 14

Acetic acid production catalyst 14 was obtained by the same procedure asExample 12, except that chromium chloride hexahydrate (0.22 g) was usedinstead of the tetrachloro aurate in Example 12.

COMPARATIVE EXAMPLE 1

A silica carrier [KA-1, particle size: 5 mmφ, product of Züd-chemie AG)(69 g) was added to an aqueous solution (45 ml) of sodiumtetrachloropalladate (1.90 g) to absorb the entire amount. This was thenadded to an aqueous solution (100 ml) of sodium metasilicate nonahydrate(5.5 g), and the mixture was allowed to stand at room temperature for 20hours. After then adding hydrazine monohydrate (5 g) thereto and gentlystirring, the mixture was allowed to stand at room temperature for 4hours for reduction to metallic palladium. After filtering the catalystand performing decantation, it was transferred to a glass columnequipped with a stopcock and purified water was passed through for 40hours at a rate of about 1.5 liters per hour for washing. This was thendried for 4 hours under an air stream at 110° C. to obtain acetic acidproduction catalyst 15.

Elemental Analysis of Acetic Acid Production Catalysts

Acetic acid production catalysts containing (a) palladium, a group (b)element and/or a group (c) element were subjected to heat treatmentusing aqua regia and/or a mixture of hydrofluoric acid and aqua regiafor complete extraction of each of the components, and measurement wasperformed by inductively coupled plasma (ICP) emission spectroscopy. TheICP emission spectroscope used was an SPS-1700 by Seiko Denshi Kogyo,KK.

The weight ratios for each of the components in catalysts 1-15 obtainedin Examples 1-14 and Comparative Example 1 and the molar ratios withrespect to Pd for each of the components are shown in Table 1. Thepercentage values in the table represent weight percentages with respectto each catalyst.

TABLE 1 Catalyst Catalyst Catalyst component component componentCatalyst No. (a) (b) (c) Catalyst 1 Pd Te (tellurium) 0.86% 0.091%(Te/Pd = 0.09) Catalyst 2 Pd Pb (lead) 0.86%  0.54% (Pb/Pd = 0.33)Catalyst 3 Pd Te (tellurium) 0.86% 0.091% (Te/Pd = 0.09) Catalyst 4 PdBi (bismuth) 0.86% 0.198% (Bi/Pd = 0.12) Catalyst 5 Pd Sn (tin) 0.86%0.180% (Sn/Pd = 0.19) Catalyst 6 Pd Te (tellurium) 1.11% 0.117% (Te/Pd =0.09) Catalyst 7 Pd Te (tellurium) 0.59% 0.062% (Te/Pd = 0.09) Catalyst8 Pd Au (gold) 0.86%  0.30% (Au/Pd = 0.19) Catalyst 9 Pd Zn (zinc) 0.86% 0.10% (Zn/Pd = 0.10) Catalyst 10 Pd Cr (chromium) 0.86%  0.07% (Cr/Pd =0.14) Catalyst 11 Pd Mn (manganese) 0.86% 0.088% (Mn/Pd = 0.20) Catalyst12 Pd Te (tellurium) Au (gold) 0.86% 0.091%  0.30% (Te/Pd = 0.09) (Au/Pd= 0.19) Catalyst 13 Pd Te (tellurium) Zn (zinc) 0.86% 0.091%  0.10%(Te/Pd = 0.09) (Zn/Pd = 0.10) Catalyst 14 Pd Te (tellurium) Cr(chromium) 0.86% 0.091%  0.09% (Te/Pd = 0.09) (Cr/Pd = 0.15) Catalyst 15Pd 0.86%

EXAMPLES 15-28 AND COMPARATIVE EXAMPLE 2

[Production of Acetic Acid]

An SUS316 reaction tube (25 mm inner diameter) was packed with 12.5 mlof each of the acetic acid production catalysts obtained in Examples1-14 and Comparative Example 1, and reaction was conducted with acatalyst bed reaction peak temperature of 160° C., a reaction pressureof 0.8 MPa (guage pressure), introduction of a gas supply comprising amixture of ethanol, oxygen, steam and nitrogen at a volume ratio of2.5:6:25:66.5 and a space velocity of 4400 hr⁻¹. The gas produced wascooled, and the condensed reaction solution that was collected wasanalyzed by gas chromatography (GC-14B, FID by Shimazu Kagaku, KK.).

The activity of each catalyst was calculated as the grams of acetic acidproduced per hour per liter of catalst (space time yield, STY), and theselectivity was calculated as the percentage of product with respect tothe starting ethanol.

The reaction results are shown in Table 2.

TABLE 2 Ethanol conversion Acetic acid Acet- STY acetic acid rateselectivity Ethyl acetate aldehyde CO₂ Ex. No. Catalyst Compositiong/hlcat % % % % % Example 15 1 Pd—Te 193 79 83 12 0.7 2.2 16 2 Pd—Pb 18670 90 11 1.0 1.8 17 3 Pd—Te 198 80 84 11 1.0 1.8 18 4 Pd—Bi 184 80 78 122.3 5.6 19 5 Pd—Sn 163 73 76 12 2.3 8.6 20 6 Pd—Te 203 82 84 11 0.8 3.021 7 Pd—Te 138 72 65 20 2.0 8.0 22 8 Pd—Au 183 83 75 14 2.0 8.2 23 9Pd—Zn 159 75 72 13 2.3 12.1 24 10 Pd—Cr 142 72 70 12 2.4 14.3 25 11Pd—Mn 168 80 74 12 0.4 10.3 26 12 Pd—Te—Au 220 88 85 5 1.0 3.0 27 13Pd—Te—Zn 244 90 92 3 1.4 3.1 28 14 Pd—Te—Cr 226 89 90 4 1.2 4.1 Comp.Ex. 2 15 Pd alone 120 54 63 7 4.5 25.0

EXAMPLE 29

A silica carrier [KA-1, particle size: 5 mmφ, product of Züd-chemie AG](69 g) was added to an aqueous solution (45 ml) of sodiumtetrachloropalladate [Na₂PdCl₄, product of Tanaka Kikinzoku] (1.90 g),to absorb the entire amount. This was then added to an aqueous solution(100 ml) of sodium metasilicate nonahydrate [Na₂SiO₃•9H₂O, product ofWako Junyaku] (3.8 g), and the mixture was allowed to stand at roomtemperature for 20 hours. After then adding hydrazine monohydrate[N₂H₄•H₂O] (5 g) thereto and gently stirring, the mixture was allowed tostand at room temperature for 4 hours for reduction to metallicpalladium. After filtering the catalyst and performing decantation, itwas transferred to a glass column equipped with a stopcock and purifiedwater was passed through for 40 hours for washing. This was then driedfor 4 hours under an air stream at 110° C. to obtain a metallicpalladium-loaded catalyst.

This metallic palladium-loaded catalyst was then impregnated with anaqueous solution (45 ml) of tungstosilicic acid n-hydrate(H₄SiW₁₂O₄₀•nH₂O: n=20-30, product of Nihon Muki Kagaku Kogyo) (44 g).The addition was performed all at once, and the mixture was gentlystirred by rotation until the solution was thoroughly absorbed (about 3minutes). After impregnation, the wet impregnated carrier was allowed tostand at room temperature for one hour. After drying in an oven for 4hours under an air stream at 110° C., it was allowed to stand overnightin a dessicator. This produced acetic acid and ethyl acetate productioncatalyst 1.

EXAMPLE 30

Acetic acid and ethyl acetate production catalyst 2 was obtained by thesame procedure as Example 29, except that tungstophosphoric acidn-hydrate (H₃PW₁₂O₄₀•nH₂O: n=20-30, product of Nihon Muki Kagaku Kogyo)(59 g) was used instead of the tungstosilicic acid n-hydrate in Example29.

EXAMPLE 31

Acetic acid and ethyl acetate production catalyst 3 was obtained by thesame procedure as Example 29, except that an aqueous solution (45 ml) ofmanganese tungstosilicate was used instead of the tungstosilicic acidn-hydrate in Example 29.

The manganese tungstosilicate aqueous solution was obtained bydissolving manganese nitrate hexahydrate [Mn(NO₃)₂•6H₂O, product of WakoJunyaku] (0.38 g) in an aqueous solution of tungstosilicic acidn-hydrate (44 g).

EXAMPLE 32

Acetic acid and ethyl acetate production catalyst 4 was obtained by thesame procedure as Example 29, except that an aqueous solution (45 ml) ofcopper tungstosilicate was used instead of the tungstosilicic acidn-hydrate in Example 29.

The copper tungstosilicate aqueous solution was obtained by dissolvingcopper nitrate trihydrate [Cu(NO₃)₂•3H₂O, product of Wako Junyaku] (0.32g) in an aqueous solution of tungstosilicic acid n-hydrate (44 g).

EXAMPLE 33

A silica carrier [CARiACT, Q-15, product of Fuji Silicia Kagaku] (55 g)was added to an aqueous solution (56 ml) of sodium tetrachloropalladate(1.90 g), to absorb the entire amount. This was then added to an aqueoussolution (100 ml) of sodium metasilicate nonahydrate (4.0 g), and themixture was allowed to stand at room temperature for 20 hours. Afterthen adding hydrazine monohydrate (5 g) thereto and gently stirring, themixture was allowed to stand at room temperature for 4 hours forreduction to metallic palladium. After filtering the catalyst andperforming decantation, it was transferred to a glass column equippedwith a stopcock and purified water was passed through for 40 hours forwashing. This was then dried for 4 hours under an air stream at 110° C.to obtain a metallic palladium-loaded catalyst.

This metallic palladium-loaded catalyst was then impregnated with anaqueous solution (56 ml) of tungstophosphoric acid n-hydrate(H₃PW₁₂O₄₀•nH₂O: n=20-30, product of Nihon Muki Kagaku Kogyo) (45 g).The addition was performed all at once, and the mixture was gentlystirred by rotation until the solution was thoroughly absorbed (about 3minutes). After impregnation, the wet impregnated carrier was allowed tostand at room temperature for one hour. After drying in an oven for 4hours under an air stream at 110° C., it was allowed to stand overnightin a dessicator. This produced acetic acid and ethyl acetate productioncatalyst 5.

EXAMPLE 34

A silica carrier [KA-1, particle size: 5 mmφ, product of Züd-chemie AG](69 g) was added to an aqueous solution (45 ml) of sodiumtetrachloropalladate [Na₂PdCl₄, product of Tanaka Kikinzoku] (1.90 g),to absorb the entire amount. This was then added to an aqueous solution(100 ml) of sodium metasilicate nonahydrate [Na₂SiO₃•9H₂O, product ofWako Junyaku] (3.8 g), and the mixture was allowed to stand at roomtemperature for 20 hours. After then adding hydrazine monohydrate(N₂H₄•H₂O] (5 g) thereto and gently stirring, the mixture was allowed tostand at room temperature for 4 hours for reduction to metallicpalladium. After filtering the catalyst and performing decantation, itwas transferred to a glass column equipped with a stopcock and purifiedwater was passed through for 40 hours for washing. This was then driedfor 4 hours under an air stream at 110° C. to obtain a metallicpalladium-loaded catalyst.

This metallic palladium-loaded catalyst was then impregnated with anaqueous solution (45 ml) of tungstosilicic acid n-hydrate(H₄SiW₁₂O₄₀•nH₂O: n=20-30, product of Nihon Muki Kagaku Kogyo) (44 g)and telluric acid [H₆TeO₆, product of Kanto Kagaku] (0.13 g). Theaddition was performed all at once, and the mixture was gently stirredby rotation until the solution was thoroughly absorbed (about 3minutes). After impregnation, the wet impregnated carrier was allowed tostand at room temperature for one hour. After drying in an oven for 4hours under an air stream at 110° C., it was allowed to stand overnightin a dessicator. This produced acetic acid and ethyl acetate productioncatalyst 6.

EXAMPLE 35

Acetic acid and ethyl acetate production catalyst 7 was obtained by thesame procedure as Example 34, except that bismuth nitrate pentahydrate[Bi(NO₃)₂•5H₂O, product of Wako Junyaku] (0.40 g) was used instead ofthe telluric acid in Example 34.

EXAMPLE 36

A silica carrier [KA-1, particle size: 5 mmφ, product of Züd-chemie AG](69 g) was added to an aqueous solution (45 ml) of sodiumtetrachloropalladate (1.90 g) and tetrachloro aurate tetrahydrate[H₄AuCl₄•4H₂O, product of Tanaka Kikinzoku] (0.50 g), to absorb theentire amount. This was then added to an aqueous solution (100 ml) ofsodium metasilicate nonahydrate (5.2 g), and the mixture was allowed tostand at room temperature for 20 hours. After then adding hydrazinemonohydrate (6.5 g) thereto and gently stirring, the mixture was allowedto stand at room temperature for 4 hours for reduction to metallicpalladium. After filtering the catalyst and performing decantation, itwas transferred to a glass column equipped with a stopcock and purifiedwater was passed through for 40 hours for washing. This was then driedfor 4 hours under an air stream at 110° C. to obtain a metallicpalladium-loaded catalyst.

This metallic palladium-loaded catalyst was then impregnated with anaqueous solution (45 ml) of tungstosilicic acid n-hydrate(H₄SiW₁₂O₄₀•nH₂O: n=20-30, product of Nihon Muki Kagaku Kogyo) (44 g).The addition was performed all at once, and the mixture was gentlystirred by rotation until the solution was thoroughly absorbed (about 3minutes). After impregnation, the wet impregnated carrier was allowed tostand at room temperature for one hour. After drying in an oven for 4hours under an air stream at 110° C., it was allowed to stand overnightin a dessicator. This produced acetic acid and ethyl acetate productioncatalyst 8.

EXAMPLE 37

Acetic acid and ethyl acetate production catalyst 9 was obtained by thesame procedure as Example 36, except that zinc chloride [ZnCl₂, productof Wako Junyaku] (0.08 g) was used instead of the tetrachloro auratetetrahydrate in Example 36.

EXAMPLE 38

A silica carrier [KA-1, particle size: 5 mmφ, product of Züd-chemie AG](69 g) was added to an aqueous solution (45 ml) of sodiumtetrachloropalladate (3.80 g) and zinc chloride (0.14 g), to absorb theentire amount. This was then added to an aqueous solution (100 ml) ofsodium metasilicate nonahydrate (8.1 g), and the mixture was allowed tostand at room temperature for 20 hours. After then adding hydrazinemonohydrate (6.5 g) thereto and gently stirring, the mixture was allowedto stand at room temperature for 4 hours for reduction to metallicpalladium. After filtering the catalyst and performing decantation, itwas transferred to a glass column equipped with a stopcock and purifiedwater was passed through for 40 hours for washing. This was then driedfor 4 hours under an air stream at 110° C. to obtain a metallicpalladium-loaded catalyst containing zinc.

This metallic palladium-loaded catalyst was then added to an aqueoussolution (45 ml) of sodium tellurite (0.27 g), to absorb the entireamount. It was then dried for 4 hours under an air stream at 110° C. toobtain a metallic palladium-loaded catalyst containing tellurium andzinc.

This metallic palladium-loaded catalyst was then impregnated with anaqueous solution (45 ml) of tungstosilicic acid n-hydrate(H₄SiW₁₂O₄₀•nH₂O: n=20-30, product of Nihon Muki Kagaku Kogyo) (24 g).The addition was performed all at once, and the mixture was gentlystirred by rotation until the solution was thoroughly absorbed (about 3minutes). After impregnation, the wet impregnated carrier was allowed tostand at room temperature for one hour. After drying in an oven for 4hours under an air stream at 110° C., it was allowed to stand overnightin a dessicator. This produced acetic acid and ethyl acetate productioncatalyst 10.

EXAMPLE 39

A silica carrier [KA-1, particle size: 5 mmφ, product of Züd-chemie AG](69 g) was added to an aqueous solution (45 ml) of sodiumtetrachloropalladate (2.76 g) and tetrachloro aurate tetrahydrate (0.78g), to absorb the entire amount. This was then added to an aqueoussolution (100 ml) of sodium metasilicate nonahydrate (8.3 g), and themixture was allowed to stand at room temperature for 20 hours. Afterthen adding hydrazine monohydrate (6.5 g) thereto and gently stirring,the mixture was allowed to stand at room temperature for 4 hours forreduction to metallic palladium. After filtering the catalyst andperforming decantation, it was transferred to a glass column equippedwith a stopcock and purified water was passed through for 40 hours forwashing. This was then dried for 4 hours under an air stream at 110° C.to obtain a metallic palladium-loaded catalyst containing gold.

This gold-containing metallic palladium-loaded catalyst was thenimpregnated with an aqueous solution (45 ml) of tungstosilicic acidn-hydrate (H₄SiW₁₂O₄₀•nH₂O: n=20-30, product of Nihon Muki Kagaku Kogyo)(24 g) and telluric acid (0.28 g). The addition was performed all atonce, and the mixture was slowly stirred by rotation until the solutionwas thoroughly absorbed (about 3 minutes). After impregnation, the wetimpregnated carrier was allowed to stand at room temperature for onehour. After drying in an oven for 4 hours under an air stream at 110°C., it was allowed to stand overnight in a dessicator. This producedacetic acid and ethyl acetate production catalyst 11.

EXAMPLE 40

Tungstophosphoric acid n-hydrate (H₃PW₁₂ O₄₀•nH₂O: n=20-30, product ofNihon Muki Kagaku Kogyo) (150 g) was dissolved in water (75 ml) toobtain a tungstophosphoric acid aqueous solution. An aqueous solution(160 ml) of cesium nitrate [CsNO₃, product of Wako Junyaku] (25 g) wasadded dropwise over 5 minutes using a dropping funnel while vigorouslystirring the tungstophosphoric acid aqueous solution, to obtain a cesiumtungstophosphate slurry-like precipitate. The slurry-like precipitatewas vigorously stirred while an acetone solution (10 ml) of palladiumacetate [Pd(OAc)₂] (11.7 g) was added dropwise over 5 minutes using adropping funnel, and then the mixture was stirred for one hour. Thesolvent was then effluxed off with a rotary evaporator, the precipitatewas removed, and this precipitate was dried for 3 hours in an oven underan air stream at 150° C. The resulting palladium-containing cesiumtungstophosphate salt was pulverized to a particle size of 3-5 mm, driedfor 3 hours under an air stream at 200° C. and subjected to 5 hours ofreduction treatment by a hydrogen stream at 250° C., to obtain aceticacid and ethyl acetate production catalyst 12

COMPARATIVE EXAMPLE 3

A silica carrier [KA-1, particle size: 5 mmφ, product of Züd-chemie AG](69 g) was added to an aqueous solution (45 ml) of sodiumtetrachloropalladate (1.90 g), to absorb the entire amount. This wasthen added to an aqueous solution (100 ml) of sodium metasilicatenonahydrate (5.5 g), and the mixture was allowed to stand at roomtemperature for 20 hours. After then adding hydrazine monohydrate (5 g)thereto and gently stirring, the mixture was allowed to stand at roomtemperature for 4 hours for reduction to metallic palladium. Afterfiltering the catalyst and performing decantation, it was transferred toa glass column equipped with a stopcock and purified water was passedthrough for 40 hours for washing. This was then dried for 4 hours underan air stream at 110° C. to obtain acetic acid and ethyl acetateproduction catalyst 13.

COMPARATIVE EXAMPLE 4

A γ-alumina carrier [NST-3, particle size: 3.2 mmφ, product of NikkiUniversal] (50 g) was added to an aqueous solution (30 ml) of sodiumtetrachloropalladate (1.90 g), to absorb the entire amount. This wasthen added to an aqueous solution (100 ml) of sodium metasilicatenonahydrate (5.5 g), and the mixture was allowed to stand at roomtemperature for 20 hours. After then adding hydrazine monohydrate (5 g)thereto and gently stirring, the mixture was allowed to stand at roomtemperature for 4 hours for reduction to metallic palladium. Afterfiltering the catalyst and performing decantation, it was transferred toa glass column equipped with a stopcock and purified water was passedthrough for 40 hours for washing. This was then dried for 4 hours underan air stream at 110° C. to obtain acetic acid and ethyl acetateproduction catalyst 14.

Elemental Analysis of Acetic Acid and Ethyl Acetate Production Catalysts

Catalysts containing (a) metallic palladium, (b) an inorganic acidand/or salt thereof and/or a group (c) element and/or a group (d)element were subjected to heat treatment using aqua regia and/or amixture of hydrofluoric acid and aqua regia for complete extraction ofeach of the components, and measurement was performed by inductivelycoupled plasma (ICP) emission spectroscopy. The ICP emissionspectroscope used was an SPS-1700 by Seiko Denshi Kogyo, KK.

The weight ratios for each of the components in acetic acid and ethylacetate production catalysts 1 to 14 obtained in Examples 29-40 andComparative Examples 3 and 4 are shown in Table 3. The percentage valuesin the tables represent weight percentages with respect to eachcatalyst. The weight percentages of the heteropoly acids are expressedin terms of the values calculated for the molecular weight of eachcorresponding anhydride. For the group (c) elements and the group (d)elements in Table 3, the molar ratios of each element with respect toelemental Pd are shown in parentheses.

TABLE 3 Catalyst Produc- compo- Catalyst Catalyst Catalyst tion nentcomponent component component catalyst (a) (b) (c) (d) Catalyst Pdtungstosilicic acid — —  1 0.58% (H₄SiW₁₂O₄₀) 32.2% Catalyst Pdtungstophosphoric acid — —  2 0.60% (H₃PW₁₂O₄₀) 33.8% Catalyst Pdmanganese salt of — —  3 0.58% tungstosilicic acid 33.0%(Mn_(0.1)H_(3.6)SiW₁₂O₄₀) Catalyst Pd copper salt of — —  4 0.60%tungstosilicic acid (Cu_(0.1)H_(2.8)PW₁₂O₄₀) 34.3% Catalyst Pdtungstosilicic acid — —  5 0.63% (H₄SiW₁₂O₄₀) 42.2% Catalyst Pdtungstosilicic acid Te —  6 0.57% (H₄SiW₁₂O₄₀) (tellurium) 33.0%  0.11%(Te/Pd = 0.09) Catalyst Pd tungstosilicic acid Bi (bismuth) —  7 0.57%(H₄SiW₁₂O₄₀)  0.23% 33.3% (Bi/Pd = 0.12) Catalyst Pd tungstosilicic acid— Au (gold)  8 0.57% (H₄SiW₁₂O₄₀) 0.20% 32.1% (Au/Pd = 0.19) Catalyst Pdtungstosilicic acid — Zn (zinc)  9 0.57% (H₄SiW₁₂O₄₀) 0.03% 31.8% (Zn/Pd= 0.10) Catalyst Pd tungstosilicic acid Te Zn (zinc) 10 1.46%(H₄SiW₁₂O₄₀) (tellurium) 0.10% 22.4% 0.062% (Zn/Pd = (Te/Pd = 0.09)0.10) Catalyst Pd tungstosilicic acid Te Au (gold) 11 1.06% (H₄SiW₁₂O₄₀)(tellurium) 0.40% 24.4% 0.063% (Au/Pd = (Te/Pd = 0.11) 0.19) Catalyst Pdcesium salt of — — 12  8.6% tungstophosphoric acid 96.0%(Cs_(2.5)H_(3.5)PW₁₂O₄₀) Catalyst Pd — — — 13 0.58% Catalyst Pd — — — 141.10%

EXAMPLES 41-52 AND COMPARATIVE EXAMPLES 5 AND 6

[Production of Acetic Acid and Ethyl Acetate]

An SUS316 reaction tube (25 mm inner diameter) was packed with 25.0 mlof each of the acetic acid and ethyl acetate production catalystsobtained in Examples 29-40 and Comparative Examples 3 and 4, andreaction was conducted with a catalyst bed reaction peak temperature of160° C., a reaction pressure of 0.8 MPa (guage pressure), introductionof a gas supply comprising a mixture of ethanol, oxygen, steam andnitrogen at a volume ration of 10:6:25:59 and a space velocity of 1800hr⁻¹. The gas produced was cooled, and the condensed reaction solutionthat was collected and its gas components were analyzed by gaschromatography (GC-14B by Shimazu Kagaku, KK., FID and TCD).

The activity of each catalyst was calculated as the grams of acetic acidand ethyl acetate produced per hour per liter of catalyst (space timeyield, STY/unit g/h•lcat), and the selectivity was calculated as thepercentage of product with respect to the starting ethanol.

The reaction results are shown in Table 4.

TABLE 4 STY (g/h · lcat) Conversion rate Selectivity (%) ProductionEthyl Acetic % Ethyl Acetic Acet- Diethyl Ex. No. catalyst acetate acidEthanol acetate acid CO₂* aldehyde ether Ethylene Ex. 41 1 172 45 63 7815 2.3 3.3 1.7 0.2 42 2 177 50 65 77 16 3.5 2.1 1.0 0.2 43 3 170 53 6574 17 3.0 3.2 2.0 0.2 44 4 170 16 60 80 11 2.9 3.2 2.0 0.2 45 5 182 3866 78 12 3.3 3.5 1.5 0.5 46 6 121 25 51 67 10 0.7 4.4 13.0 1.8 47 7 12429 50 70 12 1.0 3.1 13.0 1.0 48 8 193 47 70 78 14 2.0 1.3 1.6 1.5 49 9212 43 75 80 12 2.3 2.8 1.5 0.5 50 10 177 121 81 62 31 1.3 0.4 1.1 4.251 11 189 119 85 63 28 1.2 0.4 1.0 3.8 52 12 69 66 40 49 34 5.3 5.3 2.33.3 Comp. Ex.  5 13 30 108 49 21 56 15 8.0 0.0 0.3  6 14 42 32 30 40 2220 10.2 6.0 2.3 *CO₂: carbon dioxide

EXAMPLE 53-56

[Production of Acetic Acid and Ethyl Acetate]

An SUS316 reaction tube (25 mm inner diameter) was packed with acid andethyl acetate production catalysts 10 obtained in Example 38 (25.0 ml),and reaction was conducted with a catalyst bed reaction peak temperatureof 160° C., a reaction pressure of 0.8 MPa (gauge pressure),introduction of a gas supply comprising a mixture of ethanol, oxygen,steam and nitrogen at a volume ratio of (%) of X:6:25:(69-X) and a spacevelocity of 1800 ⁻¹. The ethanol gas concentrations (X %) are shown inTable 5.

The gas produced was cooled, and the condensed reaction solution thatwas collected and its gas components were analyzed by gas chromatography(GC-14B by FID and TCD by Shimazu Kagaku, KK.).

The activity of each catalyst was calculated as the grams of acetic acidand ethyl acetate produced per hour per liter of catalyst (space timeyield, STY), and the selectivity was calculated as the percentage ofproduct with respect to the starting ethanol.

The reaction results are shown in Table 5.

TABLE 5 Ethanol gas STY (g/h · lcat) Conversion Selectivity (%)concentration Ethyl Acetic rate (%) Ethyl Acetic Acet- Diethyl ExampleNo. (%) acetate acid Ethanol acetate acid CO₂* aldehyde ether Ethylene53 2.5 5 104 98 6 92 2.2 0.1 0.0 0.0 54 5.0 46 175 93 26 72 2.0 0.3 0.30.0 55 10 157 120 81 62 31 1.3 0.4 1.1 4.2 56 15 279 75 70 72 14 0.6 0.45.5 7.2 *CO₂: carbon dioxide

INDUSTRIAL APPLICABILITY3

As explained above, by using an acetic acid production catalyst thatcontains (b) at least one element selected from the group consisting ofGroup 14 elements, Group 15 elements and Group 16 elements of thePeriodic Table and/or (c) at least one element selected from the groupconsisting of Group 6 elements, Group 7 elements, Group 8 elements,Group 9 elements, Group 10 elements, Group 11 elements and Group 12elements of the Periodic Table, added to a metallic palladium-loadedcatalyst to prepare a catalyst for obtaining acetic acid from ethanoland oxygen, it is possible to achieve production of acetic acid withhigher space time yields, lower selectivity for carbon dioxide andacetaldehyde and minimal deterioration, and therefore at higherproduction efficiency, compared to catalysts of the prior art.

Moreover, by using an acetic acid and ethyl acetate production catalystthat contains (b) at least one compound selected from the groupconsisting of inorganic acids and salts thereof and/or (c) at least oneelement selected from the group consisting of Group 14 elements, Group15 elements and Group 16 elements of the Periodic Table and/or (d) atleast one element selected from the group consisting of Group 6elements, Group 7 elements, Group 8 elements, Group 9 elements, Group 10elements, Group 11 elements and Group 12 elements of the Periodic Table,added to a metallic palladium catalyst to prepare a catalyst forobtaining acetic acid and ethyl acetate from ethanol and oxygen, it ispossible to achieve production of acetic acid and ethyl acetate withhigher space time yields, lower selectivity for carbon dioxide andacetaldehyde and minimal deterioration, and therefore at higherproduction efficiency, compared to catalysts of the prior art.

1. A catalyst for production of acetic acid and ethyl acetate byreaction of ethanol and oxygen, comprising (a) palladium and (b) atleast one compound selected from the group consisting of heteropolyacids and salts thereof.
 2. A process for production of a catalyst forproduction of acetic acid and ethyl acetate according to claim 1, whichcomprises the following steps 1 and 2: Step 1 A step wherein (a)metallic palladium is loaded on a carrier to obtain a metallicpalladium-loaded catalyst; Step 2 A step wherein (b) at least onecompound selected from the group consisting of heteropoly acids andsalts thereof is loaded on the metallic palladium-loaded catalystobtained in step 1 to obtain a catalyst for production of acetic acidand ethyl acetate.
 3. A catalyst according to claim 1, wherein the (a)palladium is metallic palladium.
 4. A catalyst according to claim 1,wherein the heteropoly acids are selected from tungstosilicic acid,tungstophosphoric acid, molybdosilicic acid, molybdophosphoric acid,vanadotungstosilicic acid, vanadotungstophosphoric acid,vanadomolybdosilicic acid and vanadomolybdophosphoric acid.
 5. Acatalyst according to claim 1, wherein the catalyst components are heldon a carrier.
 6. A catalyst according to claim 5, wherein the carrier issilica.
 7. A catalyst according to claim 1, wherein the compositionalratio of (a) to (b) is (a) 1 gram: (b) 0.025-500 grams.
 8. A processaccording to claim 2, wherein the carrier is silica.